pl:1 the application of photoredox catalysis to new transformations in chemical synthesis
Transcript of pl:1 the application of photoredox catalysis to new transformations in chemical synthesis
RUSSIAN ACADEMY OF SCIENCES (RAS) DIVISION OF CHEMISTRY AND MATERIAL SCIENCES RAS
RUSSIAN FOUNDATION FOR BASIC RESEARCH SCIENTIFIC COUNCIL ON ORGANIC CHEMISTRY RAS
ND ZELINSKY INSTITUTE OF ORGANIC CHEMISTRY RAS
International Conference
Molecular Complexity in
Modern Chemistry
MCMC-2014
BOOK OF ABSTRACTS
September 13-19 2014
Moscow Russia
International Advisory Committee
H Alper University of Ottawa Canada
D Astruc University of Bordeaux France
J Dupont Institute of Chemistry Brazil
P J Dyson EPFL Switzerland
R G Finke Colorado State University USA
G C Fu California Institute of Technology USA
A Furstner Max Planck Institut fur Kohlenforschung Germany
V K Jain Bhabha Research Centre India
CW Jones Georgia Institute of Technology USA
P-H Leung Nanyang Technological University Singapore
C Najera Universidad de Alicante Spain
E-i Negishi Purdue University USA
L A Oro University of Zaragoza-CSIC Spain
R Poli Institut National Polytechnique France
V Snieckus Queens University Canada
M Taillefer Institut Charles Gerhardt France
A M Trzeciak University of Wroclaw Poland
Y Yamamoto Tohoku University Japan
Local Organizing Committee
ND Zelinsky Institute of Organic Chemistry RAS
M P Egorov Chairman
V P Ananikov Vice-chairman
A D Dilman
A M Sakharov
A Y Stakheev
AM Starosotnikov
A O Terentev
O V Turova
S G Zlotin
National Advisory Committee
G A Abakumov N Novgorod
I P Beletskaya Moscow
Y N Bubnov Moscow
V N Charushin Ekaterinburg
O N Chupakhin Ekaterinburg
A I Konovalov Kazan
V V Lunin Moscow
V I Minkin Rostov
O M Nefedov Moscow
V N Parmon Novosibirsk
O G Syniashin Kazan
V A Tartakovsky Moscow
B A Trofimov Irkutsk
M S Yunusov Ufa
N S Zefirov Moscow
Index
Plenary Lectures 7
Invited Lectures 22
Oral Communications 60
Posters 110
Authors Index 326
7
Plenary Lectures
8
9
PL1
THE APPLICATION OF PHOTOREDOX CATALYSIS TO NEW
TRANSFORMATIONS IN CHEMICAL SYNTHESIS
DWC MacMillan
Merck Center for Catalysis Princeton UniversityPrinceton NJ 08544
This lecture will discuss the advent and development of new concepts in chemical synthesis
specifically the combination of photoredox catalysis with organic catalysis This new approach to
ldquosynergistic catalysisrdquo will demonstrate that multiple yet separate catalytic cycles can be aligned to
generate activated intermediates that rapidly combine with each other thereby allowing new
approaches to enantioselective CndashC and C-heteroatom bond formation
We will also introduce an approach to the discovery of new chemical reactions that we term
accelerated serendipity Accidental or lsquoserendipitousrsquo discoveries have led to some of the most
important breakthroughs in scientific history many of which have directly affected human life
Given our overarching goal of developing fundamentally new and useful chemical transformations
using catalysis and by acknowledging the tremendous impact of serendipity in scientific discovery
we questioned whether this phenomenon could be forced or simulated and therefore employed as a
tool for reaction discovery
In this presentation we will describe several new transformations that have been discovered via
ldquoaccelerated serendipityrdquo that we expect will find widespread adoption throughout the field of
chemical synthesis Moreover we will further describe how mechanistic understanding of these
processes has led to the design of a valuable new yet fundamental chemical transformation
Acknowledgements Financial support was provided by NIHGMS (R01 01 GM093213-01) and kind gifts from Merck
Amgen and Abbott
10
PL2
GOLD CATALYSIS 20
ASK Hashmi
Organisch-Chemisches Institut Fakultaumlt fuumlr Chemie und Geowissenschaften Universitaumlt
Heidelberg Im Neuenheimer Feld 270 69120 Heidelberg Germany
Homogeneous catalysis by gold has developed to an important sector of catalysis research1
Initially efforts in methodology development clearly dominated in the last years also an increasing
number of applications in synthesis has been reported23
Efforts to understand the basic mechanism
of these reactions continuously accompanied the field4
For twelve years most of the reactions followed simple reaction mechanisms basing on the
interaction of one gold centre in a gold complex or organogold compound with the substrate
molecule In most of these reactions vinylgold or alkylgold intermediates are involved sometimes
also gold carbenoids
Now an entirely new family of reactions basing on the activation of the organic substrates by two
gold complexes at the same time (one -coordinated the other -coordinated) has been discovered
These open up entirely new synthetic possibilities and follow quite complex mechanisms These
mechanisms which are new to the field of organometallic chemistry will be discussed in detail
Some of the new reactions even allow positional selective CH activations of alkyl side chains as
exemplified below
The presentation will also contain results from computational chemistry
References
1 A S K Hashmi Chem Rev 2007 107 3180-3211
2 A S K Hashmi M Rudolph Chem Soc Rev 2008 37 1766-1775
3 M Rudolph A S K Hashmi Chem Soc Rev 2012 41 2448-2462
4 A S K Hashmi Angew Chem Int Ed 2010 49 5232-5241
11
PL3
HOW MUCH CATALYST DO WE NEED
C Bolm
Institute of Organic Chemistry RWTH Aachen University 52056 Aachen Germany
Various C-N- C-O- and C-C-bond forming reactions leading to cross coupling-type products can
be performed without transition metals In this presentation we will discuss cyclizations affording
benzimidazol-2-ones1 and indazoles
2 (eqs 1 and 2 respectively) Photochemical initiations (eq 3)
led us to other directions34
R1 X
NHN
O
R3
R2
N
N
R2
R3
R1
O
40 degC 24 h
X = I Br (Cl F)
(eq 1)
toluene RT 25 h
N
R2
HNR3X
N
N
R2
R3
R1 R1
TMS
O
R2
O
R1hn
CH2Cl2 RT O
O
R1R2
TMS
X = I Br
(eq 2)
(eq 3)
KOHDMSO
diamineK2CO3
Finally we will present mechanochemical activations in ball mills that allow reducing the catalyst
loadings in asymmetric organocatalyses5-7
References
1 a) Yuan Y Thomeacute I Kim S H Chen D Beyer A Bonnamour J Zuidema E Chang
S Bolm C Adv Synth Catal 2010 352 2892 b) Beyer A Reucher C M M Bolm C
Org Lett 2011 13 2876 c) Thomeacute I Bolm C Org Lett 2012 14 1892 d) Beyer A
Buendia J Bolm C Org Lett 2012 14 3948 e) Baars H Beyer A Kohlhepp S V Bolm
C Org Lett 2014 16 536
2 Thomeacute I Besson C Kleine T Bolm C Angew Chem Int Ed 2013 52 7509
3 a) Zhang H-J Becker P Huang H Pirwerdjan R Pan F-F Bolm C Adv Synth Catal
2012 354 2157 b) Becker P Priebbenow D L Zhang H-J Pirwerdjan R Bolm C J
Org Chem 2014 79 814 c) Becker P Priebbenow D L Pirwerdjan R Bolm C Angew
Chem Int Ed 2014 53 269
4 For a photochemical activation in a metal catalysis see Bizet V Buglioni L Bolm C
Angew Chem Int Ed DOI 101002anie201310790
5 a) Joumlrres M Mersmann S Raabe G Bolm C Green Chem 2013 15 612 See also in b)
Kleine T Buendia J Bolm C Green Chem 2013 15 160
6 For a video see httpwwwbeilsteintvtvpostasymmetric-organocatalysis-in-a-ball-mill
7 For a general overview see James S L Collier P Parkin I Hyett G Braga D Maini L
Jones B Friscic T Bolm C Krebs A Mack J Waddell D C Shearouse W C Orpen
G AdamsC Steed J W Harris K D M Chem Soc Rev 2012 41 413
12
PL4
ldquoMOLECULAR METATHESIS CATALYSTSrdquo AT THE DAWN OF
INDUSTRIAL IMPLEMENTATION
DE Fogg
University of Ottawa
Ruthenium-catalyzed olefin metathesis has enormous potential for impact on the chemical
enterprise in sectors ranging from pharma to specialty polymers and ldquogreenrdquo feedstocks
Phosphine-free metathesis catalysts particularly those of the Hoveyda type (HII see Figure 1)
occupy a position of increasing prominence In one of the most high-profile current applications of
metathesis chemistry transformation of seed oils into functionalized olefins HII significantly out-
performs the benchmark Grubbs catalyst GII [12]
despite the fact that the two catalysts generate a
common active species (A) Reports from pharma RampD indicate that HII also offers superior
performance in some demanding RCM applications (RCM = ring-closing metathesis)[3]
As these
and closely related molecular metathesis catalysts enter deployment in process chemistry
understanding the mechanistic basis of their performance takes on added importance
We will discuss potential contributors to the improved productivity of HII the absence of free
PCy3 the presence of the styrenyl ether ligand and operation of HII via interchange-associative
pathways The relevance of each of these factors will be considered in the context of demanding
ring-closing and cross-metathesis reactions
Figure 1 Molecular structure of an organometallic product
References
[1] Miao X Fischmeister C Dixneuf P H Bruneau C Dubois J L Couturier J L Green
Chem 2012 14 2179-2183
[2] Biermann U Bornscheuer U Meier M A R Metzger J O Schafer H J Angew Chem
Int Ed 2011 50 3854ndash3871
[3] van Lierop B J Lummiss J A M Fogg D E Ring-Closing Metathesis A How-To Guide
In Olefin Metathesis Theory and Practice Grela K Ed Wiley Weinheim 2014
13
PL5
REDUCTIONS WITH ORGANIC REAGENTS mdash THE ELECTRON AS A
CATALYST
A Studer
WWU Muenster Chemistry Germany
In the lecture reduction processes for generation of various radicals using different organic reagents
will be presented Reactions are generally conducted using stoichiometric SET-reagents However
also some catalytic variants will be presented In the presentation radical perfluoroalkylations and
azidations will be addressed Moreover the concept of using the electron as a catalyst will be
discussed and some examples provided
14
PL6
NANOELECTRONICS MOLECULAR METAL WIRES AND RELATED
MOLECULAR MATERIALS
SM Peng
Department of Chemistry National Taiwan University Taipei Taiwan
We have designed a series of new ligands such as oligo-α-pyridylamines and used them to
construct an unique class of quadruple helix of metal strings This achievement leads to a new
direction to the application of molecular wires in the nanoelectronics
The outline is as follows
I Linear Metal String Complexes (1)
Synthesis Structure Bonding
II Potential Application as Molecular Metal Wires amp Molecular Switches (2)
STM-bj Study on the Conductivity of Metal Strings
Comparative Study on the I-V Characterisics (Theory VS Experiment)
III Tuning of the Metal Strings (3-9)
Naphthyridyl Amino Ligands Low Oxidation Mixed Metal Strings
Asymmetrical Ligands Toward Molecular Rectifier
Heteronuclear Metal String Complexes
Chiral Quadruple Helixes
IV Conclusion
Fig1 Metal Strings of Oligo- -pyridylamido Ligands
1 C-Y Yeh C-C Wang Y-H Chen and S-M Peng in Redox Systems Under Nano-Space
Control Ed T Hirao Springer Germany 2006 Ch 5
2 I-W P Chen M-D Fu W-H Tseng J-Y Yu S-H Wu C-J Ku C-H Chen and S-M
Peng Angew Chem Int Ed Engl 2006 5414
3 (a) C-H Chien J-C Chang C-Y Yeh G-H Lee J-M Fang and S-M Peng Dalton Trans
2006 2106 (b) C-H Chien G-H Lee Y Song and S-M Peng Dalton Trans 2006 3249
4 M-M Rohmer I P-C Liu J-C Lin M-J Chiu C-H Lee G-H Lee M Benard X Lopez
S-M Peng Angew Chem Int Ed Engl 2007 46 3533
5 I P-C Li W-Z Wang and S-M Peng Chem Commun 2009 4323-4331
6 R H Ismayilov W-ZWang G H Lee C Y Yeh S A Hua Y Song M M Rohmer M
Beacutenard S-M Peng Angew Chem Int Ed 2011 50 2045-2048
7 I P-C Liu C-H Chen S-M Peng Bull Jpn Soc Coord Chem 2012 59 1-8
N N N N N
M M M M MX X
4
m
M = N i C o C r
m = 0 1 2 3
X = C l N C S
15
8 M-C Cheng C-L Mai C-Y Yeh G-H Lee S-M Peng Chem Commun 2013 49 7938-
7940
9 M-J Huang S-A Hua M-D Fu G-C Huang C Yin C-H Ko C-K Kuo C-H Hsu G-H
Lee K-Y Ho C-H Wang Y-W Yang I-C Chen S-M Peng C-h Chen Chem Eur J
2014 DOI 101002chem201400067
16
PL7
NEW CYCLOADDITION STRATEGIES BASED ON STRAINED AND
UNUSUAL MOLECULES
RL Danheiser
Department of Chemistry Massachusetts Institute of Technology Cambridge MA 02139 USA
Highly substituted carbocyclic and heterocyclic rings are key structural features in many
biologically significant and commercially important compounds Although classical synthetic
approaches to such compounds have generally relied on linear substitution strategies convergent
cycloaddition and annulation strategies have emerged as powerful alternative methods for the
assembly of highly substituted cyclic compounds The intrinsic convergent nature of cycloaddition
and annulation strategies facilitates the efficient assembly of highly substituted systems that would
have required long multistep routes using alternative methods
This talk will focus on the application of strained and unusual molecules as building blocks in
cycloaddition strategies for the construction of complex carbocyclic and heterocyclic compounds
The synthetic utility of highly unsaturated conjugated molecules such as vinylketenes conjugated
enynes vinylallenes allenylimines and iminoacetonitriles will be described as well as their
application in the total synthesis of natural products
17
PL8
SILICON TETHER MOTIF IN C-H ACTIVATION REACTIONS
V Gevorgyan
University of Illinois at Chicago
We have developed a set of new transition metal-catalyzed C-H activation methodologies
employing a silicon-tether motif These methods feature (a) use of silyl group as a tether between a
substrate and a reagent thus transforming intermolecular reaction into intramolecular reaction1-2
(b) employment of a silicon-tethered directing group which is traceless or easily convertable into
valuable functionalities3-8
(c) use of silyl-tethered hydrosilane reagent9-10
and (d) introduction of
new NSi-chelation concept that allows for a remote activation of aliphatic C-H bonds11
The scope of these transformations will be demonstrated and the mechanisms will be discussed
References
1 Huang C Gevorgyan V J Am Chem Soc 2009 131 10844
2 Huang C Gevorgyan V Org Lett 2010 12 2442
3 Chernyak N Dudnik A S Huang C Gevorgyan V J Am Chem Soc 2010 132 8270
4 Dudnik A S Chernyak N Huang C Gevorgyan V Angew Chem Int Ed 2010 49 8729
5 Huang C Chattopadhyay B Gevorgyan V J Am Chem Soc 2011 133 12406
6 Huang C Ghavtadze N Chattopadhyay B Gevorgyan V J Am Chem Soc 2011 133 17630
7 Gulevich A V Melkonyan F S Sarkar D Gevorgyan V J Am Chem Soc 2012 134
5528
8 Sarkar D Melkonyan F S Gulevich A V Gevorgyan V Angew Chem Int Ed 2013 52
10800
9 Kuznetsov A Gevorgyan V Org Lett 2012 14 914
10 Kuznetsov A Onishi Y Inamoto Y Gevorgyan V Org Lett 2013 15 2498
11 Ghavtadze N Melkonyan F S Gulevich A Huang C Gevorgyan V Nat Chem 2014 6
122
18
PL9
WERNER COMPLEXES A NEW CLASS OF CHIRAL HYDROGEN BOND
DONOR CATALYSTS FOR ENANTIOSELECTIVE ORGANIC REACTIONS
JA Gladysz
Department of Chemistry Texas AampM University PO Box 30012 College Station Texas 77842-
3012 USA
Salts of the chiral tris(ethylenediamine)-substituted octahedral trication [Co(en)3]3+
and related
species have played important historical roles in the development of inorganic chemistry and
stereochemistry12
As Werner described in 1912 the two enantiomers commonly designated and
can be separated by crystallization of the diastereomeric tartrate salts2 However despite the low
cost and ready availability of the building blocks there have been no applications in
enantioselective organic synthesis
NH2
NH2
H2N
H2N
NH2
H2N
Co3+
H2N
H2N
NH2
NH2
NH2
H2N
Co3+L D
We have found that [Co(en)3]
3+ and related cations can be rendered soluble in organic solvents by
using lipophilic anions such as BArfndash
3 Suitably functionalized derivatives act as highly
enantioselective catalysts for a variety of carbon-carbon bond forming reactions The mechanisms
involve outer sphere activation of the electrophile by hydrogen bonding to the NH moieties Other
types of metal-containing chiral hydrogen bond donors are also effective including a chelate of the
CpRuL fragment
H2N
H2N
NH2
NH2
NH2
H2N
Co3+ Ph
Ph
Ph
Ph
Ph
Ph
2Clndash BAr fndash
catNO2
NO2
OMe
O
MeO
O
Et3N acetone
10 molO O
OMeMeO
12 eq 0 degCX
X
Time (h)
Conversion ()
ee ()
15 gt99 88NO2
OMe
O
MeO
O
22 98 94NO2
OMe
O
MeO
O
O
Ph
H2N
H2N
NH2
NH2
NH2
H2N
Co3+ Ph
Ph
Ph
Ph
Ph
Ph
2BF4ndash BAr f
ndash
H2N
H2N
NH2
NH2
NH2
H2N
Co3+ Ph
Ph
Ph
Ph
Ph
Ph
2PF6ndash BAr f
ndash
Time (h)
Conversion ()
ee ()
10 94 90
7 98 97
Time (h)
Conversion ()
ee ()
4 gt99 86
4 gt99 94
L L L
1 Kauffman G B Coord Chem Rev 1974 12 105-149
2 Werner A Chem Ber 1911 44 1887-1898 and 1912 45 121-130
3 Ganzmann C Gladysz J A Chem Eur J 2008 14 5397-5400
4 Ghosh S K Ojeda A S Guerrero-Leal J Bhuvanesh N Gladysz J A Inorg Chem 2013
52 9369-9378
5 Thomas C Gladysz J A ACS Catalysis 2014 5 1134-1138
19
PL10
COMPLEXITY IN SIMPLICITY THE PROTOTYPE REACTIONS OF
CARBENE ANALOGS
MP Egorov
Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Prospect 47
Moscow 119991 Russia
20
PL11
SELECTIVELY ALKYLATED AND ARYLATED N-HETEROAROMATICS
VIA ACCEPTORLESS DEHYDROGENATIVE CONDENSATION
(ADC) REACTIONS
R Kempe
Lehrstuhl Anorganische Chemie II (Catalyst Design)University of Bayreuth Bavaria Germany
Dwindling reserves of crude oil and the resulting price increase of this and other fossil carbon
sources combined with environmental concerns have resulted in a call for the use of alternative
preferably renewable resources Aside from fuel ultimately a wide variety of chemical feedstocks
are derived from fossil sources Renewable lignocellulosic materials are indigestible and therefore
not useful as food products and can be processed to give alcohols and polyols These rather highly
oxidized hydrocarbons differ drastically in their chemical nature from the cracking products of
crude oil Thus there is a high demand for new reactions that utilize alcohols and convert them into
key chemicals Recently our group developed a sustainable catalytic pyrrole synthesis[1]
Secondary alcohols and amino alcohols are deoxygenated and linked selectively via the formation
of CndashN and CndashC bonds Two equivalents of hydrogen gas and two equivalents of water are
eliminated in the course of the reaction (Acceptorless Dehydrogenative Condensation ADC)
Alcohols based entirely on renewable resources can be used as starting materials The catalytic
synthesis protocol tolerates a large variety of functional groups which includes olefins chlorides
bromides organometallic moieties amines and hydroxyl groups Furthermore we have developed a
catalyst that operates efficiently under mild conditions This methodology could also be used to
synthesize selectively functionalized pyridines from alcohols[2] In the talk the development of
alcohol re-functionalization reactions and the design of catalyst systems that mediate these reactions
are discussed
[1] S Michlik R Kempe Nature Chem 2013 5 140
[2] S Michlik R Kempe Angew Chem Int Ed 2013 52 6450
21
PL12
THE CATALYST TODAY BIG BANG AND LIFE AFTER
IP Beletskaya
Lomonosov Moscow State University Department of Chemistry Moscow Russia
Nanocatalysis and catalysis by Lewis and Broensted acids will be considered in the lecture
22
Invited Lectures
23
24
IL1
CYCLIZATIONS OF ALKYNES FROM STEREOELECTRONICS TO
CASCADE TRANSFORMATIONS
IV Alabugin
Department of Chemistry and Biochemistry Florida State University Tallahassee Fl
One of the simplest organic functional groups the alkyne moiety is also one a useful starting point
for the design of cascade transformations which proceed through the formation of multiple C-C C-
H C-N and C-O bonds [1] In this talk I will illustrate how the revised stereoelectronic rules for
alkyne cyclizations [2] can be used for the bottom-up preparation of carbon nanostructures for
molecular electronics (ie graphene nanoribbons) In our approach alkyne chains of varying sizes
shapes and functionalities are built in a modular fashion and ldquozippedrdquo up into graphene
substructures via controlled cascades of all-exo or all-endo cyclizations [3]
Even in the presence of multiple functionalities alkyne cascades can be made chemoselective via
kinetic self-sorting of the pool of equilibrating radicals [4] Further synthetic opportunities are
presented by fusion of cyclization cascades with self-terminating fragmentations that allow use of
alkenes as synthetic equivalents of alkynes [5]
[1] Alabugin I V Gold B J Org Chem 2013 78 7777
[2] Alabugin I V Gilmore K Manoharan M J Am Chem Soc 2011 133 12608 Alabugin I
V Gilmore K Chem Commun 2013 49 11246
[3] Byers P M Rashid J I Mohamed R K Alabugin I V Org Lett 2012 14 6032 Byers
P J Am Chem Soc 2012 134 9609
[4] Mondal S Mohamed R K Manoharan M Phan H Alabugin I V Org Lett 2013 15
5650
[5] Mondal S Gold B Mohamed R K Alabugin I V Chemistry ndash Eur Journal 2014 in
25
IL2
ARTIFICIAL PHOTOSYNTHESIS USING TRANSITION METAL
COMPLEXES
O Ishitani
Department of Chemistry Tokyo Institute of Technology Japan
Both the problems of the global warming and shortage of the fossil fuels have brought about great
interest in photochemical utilization of CO2 with solar energy Efficient photocatalysts for CO2
reduction must be necessary for development of such an important technology
We have developed novel types of photocatalytic systems using metal complexes andor
semiconductors as a photocatalyst1 In this presentation I will focus on the architecture of two
types of the photocatalysts using transition metal complexes
(1) A mixed photocatalytic system including a ring-shaped Re(I) multinuclear complex as a
photosensitizer2
(2) Ru(II)-Re(I) and Ru(II)-Re(I) supramolecular photocatalysts3
The efficiency of the former photocatalytic system has been highest in the reported CO2-reduction
photocatalysts ( = 82) and the latter photocatalysts have been most robust (TON gt 3000)
References
1 (a) Yui T Tamaki Y Sekizawa K Ishitani O Photocatalytic reduction of CO2 from
molecules to semiconductors Top Curr Chem 2011 303 151-84 (b) Sekizawa K Maeda K
Domen K Koike K Ishitani O J Am Chem Soc 2013 135 4596
2 Morimoto T Nishiura C Tanaka M Rohacova J Nakagawa Y Funada Y Koike K
Yamamoto Y Shishido S Kojima T Saeki T Ozeki T Ishitani O J Am Chem Soc
2013 135 13266
3 (a) Gholamkhass B Mametsuka H Koike K Tanabe T Furue M Ishitani O Inorg
Chem 2005 44 2326 (b) Sato S Koike K Inoue H Ishitani O Photochem Photobiol Sci
2007 6 454 (c) Koike K Naito S Sato S Tamaki Y Ishitani O J Photochem Photobiol
A Chem 2009 207 109 (d) Tamaki Y Watanabe K Koike K Inoue H Morimoto T
Ishitani O Faraday Discuss 2012 155 115 (e) Tamaki Y Morimoto T Koike K Ishitani
O Proc Natl Acad Sci USA 2012 109 15673 (f) Tamaki Y Koike K Morimoto T
Ishitani O J Cat 2013 135 22 (g) Tamaki Y Koike K Morimoto T Yamazaki Y
Ishitani O Inorg Chem 2013 52 11902
26
IL3
A PARADIGM FOR THE PRACTICAL AND ECONOMICAL FORMATION
OF CARBONmdashCARBON AND CARBONmdashHETEROATOM BONDS
ORGANOCATALYTIC REDOX COUPLED TRANSITION METAL
CATALYZED DEHYDRATIVE BOND CONSTRUCTIONS
LS Liebeskind MG Lindale
Emory University Department of Chemistry Atlanta Georgia USA
The current world-wide focus on C-H functionalization is driven in part by the conceptual promise
of atom-efficient sustainable syntheses from readily available feedstocks Of equal conceptual
value is the dehydrative formation of CmdashC CmdashN and CmdashO bonds from common bioavailable
hydroxylic reactants like carboxylic acids alcohols and phenols Given the sustainable generation
of hydroxylic feedstocks dehydrative bond formations can impact all levels of synthesis
(commodities fine chemicals biologicals) if they are efficient economical practical and substrate
general And they are uniquely poised to contribute to the search for the sustainable conversion of
biomass to biofuels This lecture describes a paradigm for the conversion of hydroxylic reactants to
value-added CmdashC CmdashN and CmdashO products based on a practical organocatalytic redox-coupled
transition metal catalyzed dehydrative bond forming process
27
IL4
CHEMICAL SYNTHESIS USING AMPHOTERIC MOLECULES
AK Yudin
University of Toronto
Over the past seven years my lab has been exploring the use of amphoteric molecules in chemical
synthesis What started as a curiosity-driven project has turned into a sustained exploration of a
virtually untouched segment of chemistry characterized by molecules with unusual combinations of
functional groups The multifunctional nature arising from forced orthogonality enables amphoteric
molecules to participate in reactions of high atom- and step- economy thereby enabling efficient
syntheses characterized by minimal reliance on protecting groups
In this lecture I will illuminate several classes of reagents developed in our lab I will discuss the
discovery of bench-stable aldehydes equipped with a C-B bond at the alpha position These
intriguing molecules have enabled the synthesis of a rich palette of other reagents that contain
carbon-boron bonds at strategic positions With the growing repertoire of boron-containing
amphoteric molecules we are in a good position to explore ideas that range from reaction discovery
to the synthesis of boron-based biologically active compounds
I will also present the evolution of peptide macrocyclization technology driven by amphoteric
aziridine aldehydes As part of this study we are attempting to understand the conformational
preferences of peptide macrocycles As a result we are moving closer to our ultimate goal of
rationalizing the behavior of a wide range of substrate classes in our cyclization reactions as well as
understanding cellular activity of macrocycles I will conclude my talk with a discussion of our
integrative macrocyclization approaches and will present recent results of our protein crystallization
efforts
28
IL5
EMERGENT FUNCTION FROM COMPLEX ADAPTIVE CATALYSTS
VV Fokin
The Scripps Research Institute Department of Chemistry La Jolla California USA and Moscow
Institute of Physics and Technology Dolgoprudny Russia
Exploiting the versatility of catalytic processes requires rigorous interrogation of the constantly
changing environment of the catalyst Detailed understanding of critical events affecting a catalyst
such as activation and deactivation unproductive off-cycle pathways and changes in the nature of
dominant species are of critical importance The seemingly formidable challenge of controlling the
reactivity of complex catalytic systems that involve dynamic and rapidly equilibrating mixtures of
intermediates may in fact be their advantage well-defined (ie non-adaptable) catalysts are often
inefficient when compatibility with many functional groups and conditions is the goal
Examples of investigation of such catalytic reactions will be illustrated by case studies of transition
metal-catalyzed transformations of alkynes Alkynes are among the most energetic hydrocarbons
and transition metals enable selective and controlled manipulation of the triple bond revealing their
unique reactivity transformations of alkynes into heterocycles and into a variety of molecules with
new carbonndashheteroatom bonds These seemingly simple transformations involve an impressive
variety of intermediates yet proceed with high selectivity and efficiency maintaining their reactivity
in most complex environments such as the biological milieu of living organisms
29
IL6
RAPID PHOTOASSISTED ACCESS TO sp3-RICH POLYHETEROCYCLIC
SCAFFOLDS
OA Mukhina NNB Kumar WC Cronk WJ Umstead AG Kutateladze
Department of Chemistry and Biochemistry University of Denver USA
Photochemical reactions hold unparalleled promise for building prohibitively strained carbo‐ and
heterocyclic scaffolds which offer expeditious access to difficult synthetic targets not accessible via
ground state chemistry Yet photochemistry is underutilized by the synthetic community which is
especially true for Diversity Oriented Synthesis (DOS) In this context we have been developing a
new photoassisted synthetic methodology which will enhance synthetic chemistry toolbox and will
be compatible with DOS1 This new photoassisted synthetic methodology allows for rapid access
to topologically diverse polycyclic scaffolds decorated by various functional groups and
carboheterocyclic pendants rigidly or semi-rigidly held in a unique spatial configuration by these
novel core frameworks Access to such topologically diverse scaffolds is realized via key
photochemical steps and their combination with ground state reactions most prominently via the
recently discovered intramolecular cycloaddition reactions of azaxylylenes and quinomethanes
photogenerated via excited state intramolecular proton transfer Details of an experimental and
theoretical mechanistic study to gain deeper understanding of underlying processes in the excited
states will also be discussed
A typical example of rapid growth of complexity in a photoassisted synthesis of enantiopure
conformationally locked ribofuranosylamines spiro-linked to oxazolidino-diketopiperazines via a
straightforward ldquoassemblyrdquo of a threonine-based photoprecursor photochemical transformation
and a simple post-photochemical modification is shown below
[1] (a) Mukhina OA Kumar NNB Arisco TM Valiulin RA Metzel GA Kutateladze
AG Angew Chem Int Ed 2011 50 9423-9428 (b) Nandurkar NS Kumar NNB
Mukhina OA Kutateladze AG ACS Combinatorial Sci 2013 15 73-76 (c) Kumar
NNB Mukhina OA Kutateladze AG J Am Chem Soc 2013 135 9608-9611 (d)
Cronk WC Mukhina OA Kutateladze AG J Org Chem 2014 791235-1246
30
IL7
TRANSITION METAL CLUSTERS UNAVOIDABLE CONTAMINANTS OR
IMPORTANT PLAYERS IN SOLUTION
VP Ananikov
Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Prospect 47
Moscow 119991 Russia Department of Chemistry Saint Petersburg State University Stary
Petergof 198504 Russia
Application of transition metal catalysis in organic synthesis is an area of outstanding progress with
prominent achievements in carbon-carbon cross-coupling carbon-heteroatom bond formation and
atom-economic construction of organic molecules
Mechanistic studies have revealed two different frameworks for catalytic processes in solution
depending on the nature of selected system and on the type of catalyst precursor used single type
metal species catalysis or multiple metal species catalysis [1] The first type of systems is widely
utilized and it is based on well-defined metal complex with strongly bound ligands The catalyst
precursor undergoes only partial or minor chemical modifications prior entering the catalytic cycle
In this model the formation of other metal derivatives is not facilitated and the active core of the
catalyst is preserved throughout the catalytic cycle
The second model can be considered as multiple metal species catalysis (in some cases - ldquococktailrdquo
of catalysts) and involves a range of simultaneously present and dynamically interchangeable metal-
containing species such as metal complexes clusters and nanoparticles [2] Such mechanistic
picture may be expected when in situ generated catalysts are employed or upon usage of
nanoparticles as catalysts precursors
It is of much interest to reveal the role of metal clusters in these catalytic systems Formation of
clusters was detected in many cases although their role remains unclear In some cases the presence
of clusters was related to decomposition of the active form while in the other cases the formation of
dinuclear and polynuclear species is an important stage of catalyst evolution in solution
We have investigated soluble metal complexes and nanoparticles of Pd Ni Pt and Au for
development of efficient catalytic systems for selective carbon-heteroatom and carbon-carbon bond
formation in solution [3-5] Homogeneous transition-metal-catalyzed reactions and heterogeneous
nanoparticle-catalyzed reactions were considered with a focus on metal species interconversions
and nanoparticle contamination of homogeneous catalytic systems
References
[1] Kashin AS Ananikov V P J Org Chem 2013 78 11117 (doi 101021jo402038p)
[2] Ananikov V P Beletskaya I P Organometallics 2012 31 1595 (doi 101021om201120n)
[3] Zalesskiy S S Sedykh A E Kashin A S Ananikov V P J Am Chem Soc 2013 135
3550 (doi 101021ja311258e)
[4] Ananikov V P Orlov N V Zalesskiy S S Beletskaya I P Khrustalev V N Morokuma
K Musaev D G J Am Chem Soc 2012 134 6637 (doi 101021ja210596w)
[5] Kashin A S Ananikov V P Top Catal 2013 56 1246 (doi 101007s11244-013-0091-5)
31
IL8
SIMPLE COPPER CATALYSTS FOR C-C C-N AND C-O BONDS
FORMATION
F Monnier
Institut Charles Gerhardt (UMR 5253) ENSCM FRANCE
Since its renaissance in 2001 [1] the copper cross-coupling of nucleophiles with aryl halides has
been increasingly studied [2] In this account we exposed our last contribution for the formation of
C-C [3] C-N [4] and C-O [5] bonds catalyzed by a cheap and simple combination of copper salts
and -diketone ligands
1 a) M Taillefer H-J Cristau P P Cellier J-FSpindler Env SAU2001-1009 and SAU2001-
01044 patents Fr2833947-WO0353225 (Pr Nb Fr 2001 16547) M Taillefer H-J Cristau P
P Cellier J-F Spindler A Ouali Fr2840303-WO03101966 (Pr Nb Fr 2002 06717) b) S L
Buchwald A Klapars J C Antilla G E Job M Wolter F Y Kwong G Nordmann E J
HennessyWO02085838 (priority number US0286268 2001)
2 For a review see F Monnier M Taillefer Angew Chem Int Ed 2009 48 6954-697
3 a) G Danoun A Tlili F Monnier M Taillefer Angew Chem Int Ed 2012 51 12815 b)
MTaillefer F Monnier A Tlili G Danoun PCT Int Appl (2013) WO 2013 EP61697
20130606 FR20120055275 20120606
4 a) A Tlili F Monnier M Taillefer Chem Commun 2012 48 6408-6410 b) E Racine F
Monnier J-P Vors M Taillefer Chem Commun 2013 49 7412 c) E Racine F Monnier J-
P Vors M Taillefer Org Lett 2011 13 2818
5 a) A Tlili N Xia F Monnier M Taillefer Angew Chem Int Ed 2009 48 8725-8728
32
IL9
INTERACTIONS IN IONIC LIQUIDS PROBED BY NMR SPECTROSCOPY
DISTANCES CONFORMATIONS AND MORE
R Giernoth A Broehl Y Lingscheid
University of Cologne Department of Chemistry Koeln Germany
One often-mentioned aspect of ionic liquids (ILs) is that they are ldquodesigner solventsldquo whose
properties can be designed for any particular need [1] Obviously it is impossible to choose a
different property for a given IL but only a different IL entirely To be able to sensibly do so it is
necessary to know about the supramolecular structures and the governing interactions in the ionic
liquid phase
NMR spectroscopy and the nuclear overhauser effect
spectroscopy (NOE) in particular is the method of choice
for the investigation of ion pair interactions [2] The
NOE arises due to inter- and intramolecular cross
relaxation
To be able to precisely measure interactions in solution
an internal distance standard is needed We have
synthesized a monofluorinated ionic liquid which was subsequently employed in NOE-based NMR
investigations for the determination of distances and interactions in the ionic liquid phase
In a different project we are studying the influence of
different ionic liquids on peptide conformations much
in accord with the well-known Hofmeister series of ions
[3] With the help of a model system we are going to
demonstrate that the choice of ions has a strong effect on
the tertiary structure of different peptides in solution
and how these effects can be used for new non-native
peptide chemistry
References
[1] for reviews see JP Hallett T Welton Chem Rev 2011 111 3508-3576 E J Maginn J
Phys Condens Matter 2009 21 1ndash17
[2] P S Pregosin Pure Appl Chem 2009 81(4) 615ndash633 Y Lingscheid S Arenz R Giernoth
ChemPhysChem 2012 13 261ndash266
[3] F Hofmeister Arch Exp Pathol Pharmakol 1888 64 247
33
IL10
APPLICATION OF α-CF3-SUBSTITUTED DIAZOCOMPOUNDS IN
ORGANIC SYNTHESIS AND CATALYSIS
SN Osipov DV Vorobyeva IE Tsishchuk
AN Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences Moscow
An efficient pathway to multifunctional CF3-containing aromatic heteroaromatic and heterocyclic
compounds including cyclic amino carboxylic and amino phosphonic acid derivatives have been
developed The method is based on in situ generation of highly electrophilic CF3-carbene species
from the corresponding α-diazo carboxylates or phosphonates under Cu- or Rh-catalysis and their
reactions with appropriate nucleophilic partners1-4
The further applications of the reaction products in metal-catalysed transformations of different
types eg such as ring closing diene and ene-yne metathesis intramolecular Pauson-Khand
reaction as well as [2+2]-cycloaddition open an access to new families of fluorinated molecules
References
1 DV Vorobyeva AK Mailyan AS Peregudov NM Karimova TP Vasilyeva IS
Bushmarinov C Bruneau PH Dixneuf SN Osipov Tetrahedron 2011 67 3524
2 AK Mailyan IM Krylov C Bruneau PH Dixneuf SN Osipov Synlett 2011 2321
3 AK Mailyan IM Krylov C Bruneau PH Dixneuf SN Osipov Eur J Org Chem
2013 5353
4 IE Tsishchuk DV Vorobyeva AS Peregudov SN Osipov Eur J Org Chem 2014
2480
34
IL11
NEW ADVANCES IN ORGANOMETALLIC AND PHOSPHORUS
ELECTROCHEMISTRY
DG Yakhvarov OG Sinyashin
AEArbuzov Institute of Organic and Physical Chemistry Laboratory of Organometallic and
Coordination Compounds Kazan Russian Federation
The development of modern chemical science and creation of new industrially applicable
technologies are focused on application of effective and ecologically safe methods for the
preparation of important and useful chemical compounds and materials The combination of
transition-metal catalysis and organic electrosynthesis has attracted increasing attention due to the
high selectivity and efficiency of this approach in the synthetic preparation of various compounds
bearing carbon-carbon and carbon-element bonds The mild conditions single-stage process cyclic
regeneration of the catalyst and convenient and relatively inexpensive form of the energy used are
the main advantages of electrochemical methods Application of electrochemical processes to large-
scale production (macroscale synthesis) has led to significant development of the chemical
technologies of the 21st century due to easy access to highly reactive intermediates and tuning of
the reactivity of the substrate used during the synthetic process by simple adjustment of the
electrode potential
The elaborated in our research group electrochemical methods have been successfully applied for
generation of organometallic sigma-complexes1 which are important intermediates of different
carbon-carbon and carbon-element coupling processes selective preparation of organophosphorus
compounds from white phosphorus2 activation of inert oligophosphorus moieties formed in the
coordination sphere of transition metal complexes3 selective cleavage of the tungsten-phosphorus
bond resulting in valuable metal-free phosphorus heterocycles obtained via phosphinidene
intermediates4
Herein we present recent advances in synthetic application of the electrochemical techniques for
preparation and activation of organonickel complexes1 and generation of new previously known as
unstable phosphorus intermediates5 which can be applied for preparation of practically useful
organophosphorus compounds transition metal catalysts and magnetically active materials6
Acknowledgements Financial support from the Russian Scientific Fund (project 14-13-01122) and
Russian Foundation for Basic Research (project 09-03-00933-a) is gratefully acknowledged
References
[1] DGYakhvarov AFKhusnuriyalova OGSinyashin Organometallics 2014 in press
[2] DGYakhvarov EVGorbachuk OGSinyashin Eur JInorgChem 2013 4709
[3] DYakhvarov PBarbaro LGonsalvi SMantildeas SMidollini AOrlandini MPeruzzini
OSinyashin FZanobini Angew Chem Int Ed 2006 45 4182
[4] DGYakhvarov YuHBudnikova NHTran Huy LRicard FMathey Organometallics
2004 23 1961
[5] DYakhvarov MCaporali LGonsalvi ShLatypov VMirabello IRizvanov OSinyashin
PStoppioni MPeruzzini Angew ChemIntEd 2011 50 5370
[6] DYakhvarov ETrofimova OSinyashin OKataeva PLoumlnnecke EHey-Hawkins APetr
YuKrupskaya VKataev RKlingeler BBuumlchner Inorg Chem 2011 50 4553
35
IL12
TRIFLUOROMETHYLATION BY SUNLIGHT-PROMOTED
PHOTOREDOX CATALYSIS
T Koike M Akita
Tokyo Institute of Technology Chemical Resources Laboratory Yokohama Japan
Photoredox catalysis 1 mediated by photo-sensitizers (eg [Ru(bipy)3]
2+ and relevant Ir complexes)
has attracted increasing attention as practical green synthetic chemical processes because they are
visible light-promoted redox-neutral reactions
We have demonstrated that photoredox catalysis is a powerful synthetic tool in particular for
trifluoromethylation of olefinic substrates which is the topic of the presentation23
In all cases
electron transfer from the photoexcited metal species to an electrophilic CF3-reagent generates the
key CF3 radical intermediate together with the cationic species of the catalyst Subsequent
addition of the CF3 radical to the olefinic substrate followed by oxidation of the resultant carbon
radical intermediate by the cationic metal species gives the carbocationic intermediate which is
trapped by nucleophiles or deprotonated to furnish the coupling products The sequential redox
processes make the system redox-neutral It is remarkable that the reactions are promoted not only
by artificial light sources (eg Xe lamp and blue LED lamps) but also by sunlight
References 1) C K Prier D A Rankic and D W C MacMillan Chem Rev 113 5322 (2013)
2) T Koike and M Akita (a) Synlett 24 2492 (2013) (b) Topics in Cat 259 in press (2014)
(DOI 101007s11244-014-0259-7) 3) Y Yasu T Koike M Akita et al (a) Angew Chem Int
Ed 51 9567 (2012) (b) Chem Commun 49 2037 (2013) (c) Org Lett 15 2136 (2013) (d)
Org Lett 16 in press (2014) (DOI 101021ol403500y) (e) Beilstein J Org Chem submitted
(f) to be submitted see also (g) Chem Commun 48 5355 (2012) (h) ibid 49 7249 (2013)
36
IL13
CYCLIC HYPERVALENT IODINE REAGENTS A TREASURE OF
REACTIVITY FOR CATALYSIS AND SYNTHESIS
J Waser
Ecole Polytechnique Federale de Lausanne ISIC SB LCSO Lausanne Switzerland
The non-classical four electrons three centers bonds of hypervalent iodine are weaker than normal
classical bonds This confers an exceptional reactivity to these compounds as oxidants or atom-
transfer reagents Cyclic hypervalent iodine reagents are especially interesting as they combine
enhanced stability with unique opportunities for reactivity modulation In particular our group has
been interested in the development of alkynylation methods using cyclic EthynylBenziodoXolone
(EBX) hypervalent iodine reagents1 Interesting recent results of our research in the area includes
the first example of gold-catalyzed domino cyclization-alkynylation2 and a highly efficient and
practical alkynylation method for thiols3 Herein we will present our most recent work in the area
of electrophilic alkynylation as well as the extension of the use of cyclic hypervalent iodine
reagents to other functionalization reactions
References
1 JP Brand J Waser Chem Soc Rev 2012 41 4165-4179
2 Y Li J P Brand J Waser Angew Chem Int Ed 2013 52 6743-6747
3 R Frei J Waser J Am Chem Soc 2013 135 9620-9623
37
IL14
THEORY AND COMPUTATION PROVIDE INSIGHTS AND DISCOVERY
ON CHEMICAL REACTIONS OF COMPLEX MOLECULAR SYSTEMS
K Morokuma12
1 - Fukui Institute for Fundamental Chemistry Kyoto University Kyoto Japan
2 - Cherry L Emerson Center for Scientific Computation and Department of Chemistry Emory
University Atlanta GA USA
The chemical reaction that creates destroys reorganizes chemical bonds to produce new
compounds is the most important subject of chemistry Theoreticalcomputational studies have
come a long way and are now playing the central role in providing insights in understanding the
mechanism and dynamics of chemical reactions as well as in discovery of new reaction mechanisms
and reaction systems The theory can study not only the reaction of the ground state of molecules in
gas phase but also reactions of excited electronic states as well complicated reactions of complex
molecular systems The information theoreticalcomputational studies can provide is often
complementary to the information experimental studies provide and research on chemical reactions
is becoming impossible without strong collaboration between theorists and experimentalists
In the present talk I will discuss some of our recent studies of chemical reactions We have
developed the Global Reaction Route Mapping (GRRM) strategy for automatic exploration of
reaction pathways of complex molecular systems The ADDF (anharmonic downward distortion
following) and the AFIR (artificial force induced reaction) methods in the GRRM strategy have
been used for determination of not only energy minima and saddle points on the potential energy
hypersurfaces but also minima and saddle points on the conical intersection and crossing seam
hypersurfaces I will discuss the GRRM strategy and applications to several reaction systems
including photodissociation reactions catalytic reactions and enzymatic reactions
38
IL15
COMPUTATIONAL INSIGHTS INTO C-H FUNCTIONALIZATION
JUNGLE
D Musaev
Cherry L Emerson Center for Scientific Computation Emory University Atlanta Georgia USA
I will present our integrated and
collaborative approaches to the
Transition metal catalyzed C-H bond
functionalization I will elaborate our
efforts on understanding the transition
metal catalyzed C-H bond alkylation
and amination reactions and analyze
the factors controlling the reactivity of
these reactions and make intriguing
predictions I will discuss our latest
results [1] on the mono-protected amino acid ligands (MPAA) promoted Pd(II)-catalyzed
enantioselective CndashH activation reactions The presented computation allowed us to gain insights
into the mechanisms nature of active species a ligand coordination mode to the Pd(II) and
transition state structure of the CndashH activation step Our findings were supported by experiments
[1] D G Musaev T M Figg and A L Kaledin Chem Soc Rev DOI 101039C3CS60447K
(2014)
PR3
Ar
Pd
I
Ph
CsF
HCsPd
RZ ZR
Pd
ZRZR
ZR
Pd
ZR
Pd
RZ ZR
Pd
ZR
ZR
ZR ZRPd
Active
Inactive
Cs2-I-F assisted
PdNO
N
O
PG
H Ph
H
i-Pr
H
O
-
O
Ligand accelerated
Protecting Group effectBase (Cs)-effectPd-cluster effect
C-H FUNCTIONALIZATION
DIRECT Ar-Ar COUPLING
SELECTIVE RSHRSeH + C C
Pd(II)- PRECATALYST
39
IL16
A NOVEL TRIFLUOROMETHANESULFONYL HYPERVALENT
IODONIUM YLIDE FOR TRIFLUOROMETHYLTHIOLATION
N Shibata
Nagoya Institute of Technology Department of Nanopharmaceutical Sciences Nagoya Japan
In the last few decades numerous methods for the introduction of a trifluoromethylthio group into
organic compounds have been developed The main strategies are indirect methods including
halogen-fluorine exchange and trifluoromethylation of sulfur-containing compounds such as
disulfides thiols and thiolates Obviously the most attractive and ideal route to constitute the CF3S
moiety is the direct introduction of this functional group However in this approach some
limitations are usually encountered including the use of gaseous and highly toxic reagents such as
CF3SCl or unstable reagents and the modest scope of substrates Although several transition
metal-mediated or catalyzed trifluoromethylthiolation methods have been developed the substrates
are mostly limited to aromatic compounds Recently Billard and co-workers reported that
trifluoromethanesulfanylamides were effective for trifluoromethylthiolation of alkenes alkynes
indoles and organometallic species More recently Lu and Shen also developed a novel hypervalent
iodine reagent for the trifuoromethylthiolation of aryl and vinyl boronic derivatives alkynes and β-
ketoesters Even though these direct trifluoromethylthiolation reagents are shelf-stable a more
critical issue is the fact that these CF3S regents should be prepared in advance by
trifluoromethylthiolations or related trifluoromethylations Due to these limitations and negative
aspects it is thus still necessary to develop an efficient and easily available reagent to introduce the
CF3S moiety directly In contrast to the CF3S unit a trifluoromethanesulfonyl (CF3SO2) unit is
stable and often found in commonly used organic reagents such as CF3SO2Cl CF3SO2Na CF3SO2H
and (CF3SO2)2 In this context we came up with a novel idea of using ubiquitous CF3SO2
compounds as reagents for introducing the CF3S unit under reductive conditions As a part of our
recent work on the chemistry of trifluoromethanesulfonyl compounds (triflones) we herein disclose
a novel trifluoromethanesulfonyl hypervalent iodonium ylide as a shelf-stable reagent for
electrophilic-type trifluoromethylthiolation A wide variety of nucleophiles are nicely converted
into the corresponding trifluoromethylsulfanyl products by this reagent
Reference Y-D Yang A Azuma E Tokunaga M Yamasaki M Shiro N Shibata J Am
Chem Soc 135 8782 (2013)
40
IL17
CATALYSIS-ASSISTED SIGNAL ENHANCEMENT IN NUCLEAR
MAGNETIC RESONANCE
IV Koptyug
International Tomography Center SB RAS Novosibirsk Russia
When parahydrogen (nuclear spin isomer of H2) is used in catalytic hydrogenations instead of
normal H2 the NMR signals of reaction products and intermediates can be enhanced by 3-4 orders
of magnitude and more owing to the phenomenon of parahydrogen-induced polarization (PHIP)
This possibility has been explored previously in the context of activation of H2 by transition metal
complexes and clusters in solution It has been shown that PHIP can help to detect reaction products
and short-lived intermediates not detectable by conventional NMR As most of the industrial
catalytic processes are heterogeneous it would be desirable to employ PHIP in the NMR studies of
heterogeneous catalysts and catalytic reactions The objective of our research is thus to extend the
scope of PHIP applications to the heterogeneously (HET) catalyzed hydrogenation reactions and to
develop a hypersensitive NMR-based technique for the in situ and operando studies of
heterogeneous catalytic processes In addition HET-PHIP can be employed to produce catalyst-free
hyperpolarized liquids and gases for novel MRI applications including the advanced in vivo studies
We demonstrate that similar to their homogeneous counterparts heterogenized transition metal
complexes are able to produce strong NMR signal enhancements when parahydrogen is used in the
hydrogenation reactions [1] Our recent results show that various immobilized metal complexes are
can produce HET-PHIP both in liquid phase and in gas phase hydrogenations In contrast for
supported metal catalysts (eg PtAl2O3) dissociative hydrogen chemisorption and rapid migration
of H atoms on the metal surface were expected to make the required pairwise hydrogen addition to
a substrate molecule impossible Nevertheless we have shown that PHIP can be successfully
observed both in liquid-solid and in gas-solid heterogeneous hydrogenations catalyzed by supported
metal catalysts [1] The NMR signal enhancement was found to be sensitive to the metal
nanoparticle size and shape the nature of the metal and support and the type of substrate used in
the reaction Recently HET-PHIP effects were also demonstrated for several metal oxides and bulk
unsupported metals used as hydrogenation catalysts [2] The implications of these results for the
mechanisms of heterogeneous hydrogenation processes are discussed [13] Further potential
extensions of the technique will be presented including the use of metal-free catalysts for activating
parahydrogen [4] and the prospects of using nuclear spin isomers of molecules other than H2 to
further extend the range of reactions and processes that can be explored in detail using the PHIP
technique [5] In addition to applying HET-PHIP to the mechanistic and kinetic studies of
heterogeneous hydrogenations several MRI applications of HET-PHIP have been already
demonstrated including MR imaging of a catalytic reaction in an operating model microreactor [6]
1 KV Kovtunov VV Zhivonitko IV Skovpin DA Barskiy IV Koptyug Top Curr Chem 338 123
(2013)
2 KV Kovtunov DA Barskiy OG Salnikov AK Khudorozhkov VI Bukhtiyarov IP Prosvirin IV
Koptyug Chem Commun 50 875 (2014)
3 OG Salnikov KV Kovtunov DA Barskiy AK Khudorozhkov EA Inozemtseva IP Prosvirin VI
Bukhtiyarov IV Koptyug ACS Catal 4 2022 (2014)
4 VV Zhivonitko V-V Telkki K Chernichenko TJ Repo M Leskela V Sumerin IV Koptyug J
Amer Chem Soc 136 598 (2014)
5 VV Zhivonitko KV Kovtunov PL Chapovsky IV Koptyug Angew Chem Int Ed 52 13251
(2013)
6 VV Zhivonitko V-V Telkki IV Koptyug Angew Chem Int Ed 51 8054 (2012)
41
IL18
-BOND ACTIVATION REACTION BY TRANSITION METAL AND MAIN-
GROUP ELEMENT COMPOUNDS AND CATALYTIC REACTION
INCLUDING IT
S Sakaki
Fukui Institute for Fundamental Chemistry Kyoto University Takano Sakyo-ku Kyoto 606-8103
Japan
The -bond activation by transition metal complexes attracts a lot of interests in theoretical and
organometallic chemistries because it is crucial in many catalytic reactions by transition metal
complexes In our understanding -bond activation is classified to two categories the concerted
oxidative addition to M (metal) the stepwise oxidative addition via nucleophilic attack the
oxidative addition to M-L (L = neutral ligand) and the heterolytic activation by M-X (X = anionic
ligand) activation by metal center only and that by the metal-ligand moiety12
MLn + R1-R2 cis-MLn(R1)(R
2) (1)
MLn + R1-X [MLn(R1)] --(X) trans-MX(R
1)Ln (2)
MLLn + R1-R2 MLn(R1)(L-R
2) (3)
MXLn + R1-R2 MLn(R1) + R
2-X (4)
We theoretically investigated these reactions and elucidated the characteristic electronic processes
and clear understanding2 We also theoretically investigated catalytic reactions including -bond
activation In this talk we wish to present our recent theoretical studies of carboxylation of
phenylchloride catalysed by a nickel(0) complex hydrosilylation of carbon dioxide catalyzed by
germanium(II)- and zinc(II)-hydride compounds3
In my talk I wish to present comprehensive understanding of these -bond activation reactions and
the importance of -bond activation reaction in such catalytic reactions as CO2 conversion and
cross-coupling reactions
References
1 S Sakaki Y-y Ohnishi H Sato Chem Record 10 29 (2010) W Guan F B Saeed S
Sakaki Inorg Chem in press
2 N Ochi Y Nakao H Sato S Sakaki J Am Chem Soc 129 8615 (2007) N Ochi Y Nakao
H Sato S Sakaki J Phys Chem A 114 659 (2010)
3 N Takagi and S Sakaki J Am Chem Soc 135 8955 (2013) M Deschmukh to be submitted
42
IL19
NONPLANAR HETEROAROMATICS SYNTHESIS AND SELF-ASSEMBLY
M Stepien
Wydziaі Chemii Uniwersytet Wrocіawski
Even though π-electron aromaticity is typically associated with planar structures several classes of
distorted π-aromatics are known including a variety of twisted helical bowl-shaped or tubular
systems Such distortions are of fundamental interest because they provide a means of testing
different aspects of aromaticity theory but they also may have practical consequences as a
potential method of fine-tuning the electronic structure and self-assembly properties of aromatic
compounds
In this contribution two synthetic approaches to nonplanar heteroaromatics will be discussed One
is based on oxidative coupling reactions of pyrrole-containing precursors and is exemplified by our
recent syntheses of peripherally fused porphyrin derivatives1 (1 and 2) and bipyrroles
2 Compounds
1ndash2 are characterized by bathochromically shifted electronic absorptions and very high extinction
coefficients Phenanthroporphyrins 1 and their complexes reveal substitution-dependent aggregation
in solution and form columnar mesophases in the condensed phase The zinc(II) complex of
benzochrysenoporphyrin 2 was found to form a unique 3D-ordered mesophase containing discrete
multiporphyrin aggregates
The other approach to nonplanar aromatics explored in our laboratory which is suitable to the
synthesis of bowl- or belt-shaped structures involves the so-called fold-in synthesis3 performed on
appropriately designed macrocyclic precursors The fold-in concept can be realized using different
reactivity types including Ullmann-type reductive coupling as in the recent synthesis of
chrysaorole (3)34
and FriedelndashCrafts alkylation5
(1) Myśliwiec D Donnio B Chmielewski P J Heinrich B Stępień M J Am Chem Soc
2012 134 4822ndash4833
(2) Gońka E Myśliwiec D Lis T Chmielewski P J Stępień M J Org Chem 2013 78
1260ndash1265
(3) Stępień M Synlett 2013 24 1316ndash1321
(4) Myśliwiec D Stępień M Angew Chem Int Ed 2013 52 1713ndash1717
(5) Kondratowicz M Myśliwiec D Lis T Stępień M in preparation
43
IL20
RHODIUM N-HETEROCYCLIC CARBENE COMPLEXES AS EFFICIENT
CATALYSTS FOR X-H ADDITIONS TO ALKYNES THE QUEST FOR
SELECTIVITY
R Castarlenas A Di Giuseppe L Rubio-Perez L Palacios R Azpiroz V Polo JJ Perez-
Torrente LA Oro
ISQCH Universidad de Zaraaragoza-CSIC
The development of new catalytic systems for the synthesis of added-value products in a selective
manner and with high atom economy is nowadays an important task In this context our group has
recently prepared new rhodium complexes bearing an N-heterocyclic carbene (NHC) ligand that
have been disclosed to be very active and gem-selective for X-H additions across C-C triple
bonds1-4
Experimental and theoretical (DFT) mechanistic studies indicate that the presence of a
bulky powerful electron-releasing NHC and the rational choice of the auxiliary ligands is essential
in order to control the selectivity towards the formation of Markonikov-type products
1 A Di Giuseppe R Castarlenas JJ Perez-Torrente M Crucianelli V Polo R Sancho FJ
Lahoz LA Oro J Am Chem Soc 2012 134 8171
2 L Palacios MJ Artigas V Polo FJ Lahoz R Castarlenas JJ Perez-Torrente LA Oro ACS
Catal 2013 3 2910
3 L Rubio-Peacuterez R Azpiacuteroz A Di Giuseppe V Polo R Castarlenas JJ Perez-Torrente LA
Oro Chem Eur J 2013 19 15304
4 R Azpiacuteroz A Di Giuseppe R Castarlenas JJ Perez-Torrente LA Oro Chem Eur J 2013
19 3812
44
IL21
CATALYTIC OLEFINATION REACTION ndash UNIVERSAL METHOD FOR
SYNTHESIS OF ALKENES
VG Nenajdenko
Moscow State University Department of Chemistry Leninskie Gory Moscow 119992
Catalytic olefination reaction represents new approach to the preparation of double C=C bond N-
unsubstituted hydrazones can be converted into alkenes by treatment with polyhalogenated alkanes
in presence of a base and catalytic amounts of copper salts The reaction has a wide synthetic scope
allowing to prepare both alkyl and aryl halogenoalkenes including fluorinated ones and derivatives
with functional groups Simple experimental procedure which does not require using of
organometallic or toxic organophospourous compounds affordable price and availability of starting
materials high yields and stereoselectivity are distinct advantages of the reaction
R2
R1
COOR
Cl
R2
R1
Cl
CN
R2
R1
F
F
O
R2
R1
R2
R1
Cl
Cl
R2
R1
Br
Br
R2
R1
CH2OH
Cl
R2
R1
CClF2
F
R2
R1
CF3
Cl
R2
R1
Cl
F
R2
R1
CBrF2
F
CBrF2R
R2
R1
CBrF2
F
F
R2
R1
CONR2
Cl
R2
R1
Cl
O
O
R2
R1
I
H
R2
R1
Cl
H
R2
R1
Br
H
45
IL22
HOW TO MAKE COMPLEX MOLECULES FROM SIMPLE STARTING
MATERIAL THE PALLADIUM A POWERFUL TOOL
J Suffert
University of StrasbourgCNRS
In addition to molecular complexity the challenge of the chemist today is also the quest for
efficiency of the synthetic route and maximization of structural complexity Our laboratory
investigations focus for several years on the study of an unprecedented cascade reaction involving a
rare 4-exo-dig cyclocarbopalladation followed by a terminated cross-coupling with an
organometallic reagent A 6 - or 8 -electrocyclization can occur leading to new tricyclic structures
The seminar will show that we can offer an easy access to complex polycyclic molecules resulting
from readily available simple starting materials Eventually it will be possible to propose the
elaboration of a large collection of unprecedented structurally novel molecules based on recent
promising results Below are represented several complex structures that has been prepared through
the powerful 4-exo-dig cyclocarbopalladation Many other extension of this method have not been
so far explored and can afford a multitude of new and original scaffolds
46
IL23
SYNTHESIS OF TIN AND LEAD ANALOGS OF CYCLOPENTADIENYL
ANION AND THEIR APPLICATION TO TRANSITION-METAL
COMPLEXES
M Saito
Department of Chemistry Graduate School of Science and Engineering Saitama University
Shimo-okubo Sakura-ku Saitama-city Saitama 338-8570 Japan
We succeeded in the generation of tetraphenyldilithiostannole 1a[1]
and its considerable aromatic
character was established by X-ray diffraction analysis and theoretical calculations[2]
The lead
analog tetraphenyldilithioplumbole 2 was also found to be aromatic indicating that the concept of
aromaticity is expanded to lead-bearing carbon cycles[3]
After the synthesis of heavier congeners of Cp anion attention was next paid to the preparation of
transition-metal complexes with such heavier Cp ligands The first heavier metallocene was a
ruthenocene bearing a germole ligand[4]
and transition-metal complexes with silole and germole
ligands have already been synthesized The straightforward method for the synthesis of such
metallocenes is the reactions of metallole anions and dianions with transition-metal reagents
However the reactions using stannole anions and dianions had never been reported until recently
We examined the reaction of tetraphenyldilithiostannole 1b[5]
with [CpRuCl]4 and butterfly
complex 3 was obtained instead of an expected ruthenocene[6]
The reaction of 1b with Cp2TiCl2
afforded three-membered ring compound 4 with unique electronic states[7]
The synthesis of the first
neutral triple-decker complex 5 with group 14 metallole ligands was also achieved using silyl-
substituted dilithiostannole 1c
M
R2
R2
R1
R1
L i
L i
M = S n R1
= R2
= P h
M = S n R1
= R2
= E t
M = S n R1
= M e 3S i R2
= P h
M = P b R1
= R2
= P h
1 a
1b
1c
2
R u
R u
S n S n
E tE t
E t
E t
E t
E t
E t
E t
C p
C p
3
T i
S n
S nC p
C p
4
S n
S iM e 3
M e 3S i
P h
P h
R u C p C p R u
5
References
[1] Saito M Haga R Yoshioka M Chem Commun 2002 1002
[2] Saito M Haga R Yoshioka M Ishimura K Nagase S Angew Chem Int Ed 2005 44
6553
[3] Saito M Sakaguchi M Tajima T Ishimura K Nagase S Hada M Science 2010 328
339
[4] Freeman W P Tilley T D Rheingold A L Ostrander R L Angew Chem Int Ed Engl
1993 32 1744
[5] Saito M Kuwabara T Kambayashi C Yoshioka M Ishimura K Nagase S Chem Lett
2010 39 700
[6] Kuwabara T Saito M Guo J D Nagase S Inorg Chem 2013 52 3585
[7] Kuwabara T Guo J D Nagase S Saito M Angew Chem Int Ed 2014 53 434
47
IL24
NEW METHODS FOR PEROXIDE SYNTHESIS
AO Terentev
ZIOCh Moscow Russia
In the last decades organic peroxides have received considerable attention from chemists and drug
design experts which is associated with a need in the search for drugs for the treatment of parasitic
diseases such as malaria and helminth infections Considerable progress has been made in the
design of effective peroxide antimalarial drugs Some synthetic peroxides exhibit activity equal to
or higher than that of artemisinin Peroxides having antitumor or growth-regulatory activity were
also documented In our work we developed new methods for synthesis of various types of
peroxides
It was found that some peroxides posesses pronounced antischistosomal properties and anticancer
activity This work is supported by the Grant of the Russian Foundation for Basic Research (Grant
14-03-00237) and by the Program for Basic Research of the Presidium of the Russian Academy of
Sciences
References
[1] Terentev A Borisov D Yaremenko I Chernyshev V Nikishin G JOrgChem 75 5065-
5071 2010
[2] Terentev A Yaremenko I Chernyshev V Dembitsky V Nikishin G JOrgChem 77
1833-1842 2012
[3] Ingram K Yaremenko IA Krylov I Hofer L Terentev A O Keiser J JMedChem 55
(20) 8700ndash8711 2012
[4] Terentev A O Yaremenko I A Vil V A Dembitsky V M Nikishin G I Synthesis
246-250 2013
[5] Terentev A O Yaremenko I A Vil V A Моisееv I K Konrsquokov S A Dembitsky V
M Levitsky D O Nikishin G I Org Biomol Chem 11 2613ndash2623 2013
[6] IA Yaremenko AO Terentrsquoev VA Vilrsquo RA Novikov VV Chernyshev VA Tafeenko
DO Levitsky F Fleury GI Nikishin Chemistry - A European Journal DOI
101002chem201402594
48
IL25
SYNERGISM BETWEEN THEORY AND EXPERIMENTS IN
ASYMMETRIC CATALYSIS TRANSITION STATE MODELING FOR
RATIONALIZATIONS AND CATALYST DESIGN
RB Sunoj
Department of Chemistry Indian Institute of Technology Bombay Powai Mumbai 400076
Computational quantum chemistry has been increasingly employed toward rationalizing the
stereochemical outcome of a diverse range of reactions1 The approach typically involves the
identification of kinetically significant transition states and intermediates In our laboratory ab
initio as well as DFT methods are employed to gain insights into carbon-carbon and carbon-
heteroatom bond-forming reactions of immediate practical significance2 The key objective is in
establishing the factors responsible for stereoselectivity in such reactions and to employ those
insights toward in silico design of novel catalysts for potential asymmetric applications3
A number of examples wherein the conventional transition state models required systematic
improvements toward accounting the observed product distribution and stereochemical outcome
will be presented In general the presentation would encompass a few contemporary themes in the
domain of organo- and organo-metallic catalysis Interesting interpretationsrationalizations of
experimental observations besides meaningful guidelines for rational improvements in asymmetric
catalysis would remain the key focus of the presentation The contents are designed to cater to a
broad and diverse group of audience hence the chemical insights would receive more emphasis
rather than intricate technical details
[1] (a) Cheong P H ndashY Legault C Y Um J M Celebi-Olcum N Houk K N Chem Rev
2011 111 5042 (b) Sunoj R B Wiley Interdisciplinary Reviews Comput Mol Sci 2011 1
920
[2] (a) Shinisha C B Sunoj R B J Am Chem Soc 2010 132 12135 (b) Sharma A K
Sunoj R B Angew Chem Int Ed 2010 49 9373 (c) Sharma A K Sunoj R B Chem
Commun 2011 47 5759 (d) Jindal G Sunoj R B Chem Eur J 2012 18 7045 (e) Jindal
G Sunoj R B Angew Chem Int Ed 2014 53 4432 (f) Anand M Sunoj R B Schaefer
H F J Am Chem Soc 2014 136 5535
[3] (a) Shinisha C B Sunoj R B Org Biomol Chem 2007 5 1287 (b) Shinisha C B Sunoj
R B Org Lett 2009 11 3242 (c) Jindal G Sunoj R B Org Bimol Chem 2014 12 2745
49
IL26
CATALYTIC ASYMMETRIC CROTYLATION METHOD DEVELOPMENT
AND APPLICATION IN TOTAL SYNTHESIS
AV Malkov PS Orsquohora CA Incerti-Pradillos MA Kabeshov
Loughborough University Loughborough LE11 3TU UK
Secondary metabolites 1-5 isolated from marine soft coral Pseudopterogorgia elisabethae exhibit a
wide range of useful biological properties which include anti-tubercular anti-inflammatory
antimicrobial and analgesic activities [1] The analgesic properties are superior to the existing
industry standards As a result partially purified gorgonian extracts are used in commercial skin
care products for topical applications [2]
H
OH
HO
Pseudopterosin A-Daglycone
H H
O
O
HO
H
OH
O
O
H
O
O
HO
HH
1 2 3 4
(ndash)-Elisapterosin B (ndash)-Colombiasin A(+)-Elisabethadione(+)-Erogorgiaene
5
Herein we present a novel general strategy for a scalable enantioselective total synthesis of
serrulatane diterpenes 1 and 2 Synthetically a major challenge associated with the synthesis of
these compounds is the control of the three stereocentres in the absence of directing functional
groups Our principal strategy is based on the asymmetric crotylation of cinnamyl-type aldehyde 10
with Z-crotyltrichlorosilane 9 to produce homoallylic alcohol 8 with a set of stereogenic centers that
will be used to control the stereochemistry of oxy-Cope rearrangement (8 rarr 7) and the subsequent
transformations towards the advanced intermediate 6 Development of novel efficient Lewis base
catalysts for the asymmetric crotylation and completion of the total synthesis of (ndash)-elisabethadione
and (ndash)-erogorgiaene will be discussed in detail
SiCl3O
OH
Cat
H
O
Anionic oxy-Cope
H
OH6
cationic cyclisation
Wittigolefination
12
7
810
Rn
Rn
RnRn
1
4
11
9
References
[1] A D Rodriguez C Ramirez J Nat Prod 2001 64 100-102
[2] A Kijjoa P Sawanwong Mar Drugs 2004 2 72-82
50
IL27
SYNTHESES OF METAL COMPLEXES WITH TRANS-CYCLOALKANE-
12-DIYL-[OSSO]-TYPE BIS(PHENOLATE) LIGAND AND ISOSPECIFIC
POLYMERIZATION OF ALPHA-OLEFINS
A Ishii
Department of Chemistry Graduate School of Science and Engineering Saitama University
Shimo-okubo Sakura-ku Saitama 338-8570 Japan
Efficiency and stereoselectivity of reactions catalyzed by metal complexes are often greatly affected
by auxiliary ligands of the catalysts We have recently developed tetradentate auxiliary ligands 1
featuring oxygen and sulfur coordination sites and fusion of trans-cycloalkane-12-diyl rings1ndash3
The
[OSSO]-bis(phenolate) ligand 1 (n = 3) was applied to the synthesis of zirconium complex 2 and we
found that a combination of 2 and an activator catalyzes the polymerization of 1-hexene with high
activity and high isospecificity1 in comparison with previously reported group 4 metal complexes
bearing [OSSO]-type ligands4 We have also synthesized Ti
5 Zr
6 Hf
7 V
8 Nb
8 Ta
8 and Al
9
complexes with 1 (n = 3) and investigated catalytic reactions with these complexes In this paper
we report the syntheses and structures of these metal complexes and their catalytic ability with
recent progress
S
SO
tBu
tBu
O
tBu
tBu
ZrCH2Ph
CH2Ph
1 2
S OH
tBu
tBu
OH
tBu
tBu
Sn
Bu 2(Ph3C)[B(C6F5)4] Bu Bu Bu Bu Bu
isotactic poly(1-hexene) ([mmmm] gt95)
activity =
2500 gbullmmolndash1bullhndash1
Mw = 59000 PDI = 17
References
1 Ishii A Toda T Nakata N Matsuo T J Am Chem Soc 2009 131 13566ndash13567
2 Ishii A Toda T Nakata N Matsuo T Phosphorus Sulfur Silicon 2011 186 1169ndash1174
3 Ishii A Asajima K Toda T Nakata N Organometallics 2011 30 2947ndash2956
4 Nakata N Toda T Ishii A Polym Chem 2011 2 1597ndash1610
5 Nakata N Toda T Matsuo T Ishii A Inorg Chem 2012 51 274ndash281
6 Toda T Nakata N Matsuo T Ishii A J Organomet Chem 2011 696 1258ndash1261
7 Nakata N Toda T Matsuo T Ishii A Macromolecules 2013 46 6758ndash6764 Nakata N
Saito Y Watanabe T Ishii A Top Catal 2014 57 918ndash922
8 Toda T Nakata N Matsuo M Ishii A ACS Catal 2013 3 1764minus1767
9 Nakata N Saito Y Ishii A Organometallics 2014 33 1840ndash1844
51
IL28
NEW APPROACH FOR THE SYNTHESIS OF COMPOUNDS CONTAINING
CF2 FRAGMENT
AD Dilman VV Levin AA Zemtsov MD Kosobokov
N D Zelinsky Institute of Organic Chemistry
Existing methods for the synthesis of compounds containing CF2 fragment either employ hazardous
reagents or require long synthetic sequence We propose a new approach towards difluorinated
compounds based on the coupling of three components mdash nucleophile difluorocarbene and
electrophile
As nucleophiles organometallic reagents can be employed The insertion of difluorocarbene into
carbon-zinc bond of organozinc reagents leads to new organozinc species which can be quenched
by halogen or proton1 or coupled with allylic electrophiles
2
The interaction of trimethylsilyl cyanide with difluorocarbene affords difluoro(trimethylsilyl)-
acetonitrile This reagent was used in reactions with aldehydes and imines furnishing fluorinated
alcohols and amines3 The addition products can be transformed into a variety of heterocyclic
molecules4
This work was supported by the Ministry of Science (project MD-475020133) and Russian
Foundation for Basic Research (projects 13-03-12074 14-03-00293 14-03-31253_mol_a 14-03-
31265_mol_a)
1 Levin V V Zemtsov A A Struchkova M I Dilman A D Org Lett 2013 15 917ndash919
2 Zemtsov A A Kondratyev N S Levin V V Struchkova M I Dilman A D J Org
Chem 2014 79 818ndash822
3 Kosobokov M D Dilman A D Levin V V Struchkova M I J Org Chem 2012 77
5850ndash5855
4 Kosobokov M D Struchkova M I Arkhipov D E Korlyukov A A Dilman A D
J Fluorine Chem 2013 154 73ndash79
52
IL29
TOWARDS REALISTIC FIRST-PRINCIPLES MODELLING OF
COMPLEXITY IN HETEROGENEOUS CATALYSIS
KM Neyman
ICREA and Universitat de Barcelona
Active components present in heterogeneous catalysts as nano-aggregates of thousands atoms
remain inaccessible for the first-principles (based on DFT) computations due to their size and
complexity However such species could be rather realistically represented by computationally
tractable smaller model nanoparticles (NPs) whose surface sites only marginally change the
reactivity with increasing particle size We illustrate this for decomposition of methane1 and
methanol2-4
on Pt and Pd catalysts as well as building of active sites on Ptceria catalysts56
We
show that using common slab models and thus neglecting the nanoscopic effects in these and
similar systems could lead to severe misrepresentation of the surface reactivity7
Methane decomposition on Pt NP is calculated to be more exothermic than on Pt(111) surface and
proceed via much lower activation barriers for the rate-limiting steps1 The reason for Pt activation
by nanostructuring is that CHx species are stabilized on NP edges converting the first two steps of
CH4 decomposition from endothermic on Pt(111) to exothermic on Pt79 The higher activity of edge
Pt atoms was assigned to their lower coordination and higher flexibility
The flexibility affects not only adsorption properties of sites with low-coordinated atoms but also
nearby terrace sites This effect is most pronounced for strongly bound adsorbates eg atomic C It
is a common by-product in decomposition reactions on Pd2 able to modify catalyst properties upon
exothermic migration subsurface34
The most spectacular effect of flexibility of Pd NPs is on the
subsurface migration barriers of surface C Near NPs edges these barriers essentially vanish
Presence of subsurface C makes Pd NPs more transparent for subsurface diffusion of adsorbed
hydrogen3 which in turn enables sustainable hydrogenation of olefins on Pd catalysts
Strong metal-support interactions can radically modify surface chemistry Due to catalysts
complexity the microscopic origin of such effects is usually unresolved However our study on
models of Pt-ceria catalysts succeeded to uncover atomic details of interactions in this system5
Calculations identified two types of oxidative Pt-ceria interactions electron transfer from a Pt
particle to the support and O transport from ceria to Pt The former is favorable on ceria supports
regardless their morphology But the O transfer requires the presence of Pt in close contact with
nanostructured ceria being inherently a nano-effect Both effects were detected by monitoring the
Ce3+
Ce4+
ratio using resonant photoelectron spectroscopy on Pt-CeO2 model catalysts
These case studies reveal very significant differences in the surface reactivity derived from
customary slab-model calculations and those employing dedicated NP models The latter expose a
variety of active sites whose structure and geometric flexibility notably better match those of the
sites present under experimental conditions Thus we advocate much broader usage of suitable NP
models in ldquocatalysis from first principlesrdquo 1 F Vintildees Y Lykhach T Staudt M P A Lorenz C Papp H-P Steinruumlck J Libuda K M Neyman A Goumlrling -
Chem Eur J 2010 16 6530
2 I V Yudanov A V Matveev K M Neyman N Roumlsch - J Am Chem Soc 2008 130 9342
3 K M Neyman S Schauermann - Angew Chemie Int Ed 2010 49 4743
4 H A Aleksandrov F Vintildees W Ludwig S Schauermann K M Neyman - Chem - Eur J 2013 19 1335
5 G N Vayssilov Y Lykhach A Migani T Staudt G P Petrova N Tsud T Skaacutela A Bruix F Illas K C Prince
V Matoliacuten K M Neyman J Libuda - Nature Mater 2011 10 310
6 A Bruix Y Lykhach I Matoliacutenovaacute A Neitzel K C Prince V Potin F Illas V Matoliacuten J Libuda K M
Neyman et al - Angew Chemie Int Ed 2014 53 doi 101002anie201402432
7 S M Kozlov K M Neyman - Top Catal 2013 56 86
53
IL30
С-С TRIPLE BOND ACTIVATION BY PLATINUM METALS UNDER
HOMO- AND HETEROGENEOUS CONDITIONS DESIGN OF NEW
CATALYTIC REACTIONS
SA Mitchenko
LM Litvinenko Institute of Physical Organic and Coal Chemistry National Academy of Sciences
of Ukraine Donetsk Ukraine
Petroleum and natural gas are the main sources of raw materials for modern bulk and fine chemical
industry Since the middle of the last century this changed the industry redirecting technology
previously based on acetylene towards olefinic stuff and synthesis gas Nevertheless series of large-
scale (for example manufacture of vinyl ethers pyrrolidone and N-methylpyrrolidone butanediol
etc) and fine (drugs and fragrances crop protecting agents etc) chemical production based on
acetylene hydrocarbons possesses definite advantages and is still developing Besides acetylene
hydrocarbons are inevitably formed as by-products in oil processing yielding olefins and taking
into account the modern industrial scales and prices of starting materials these by-products should
be efficiently utilized On the other hand coal and natural gas supply as against of petroleum allow
us to regard them as practically inexhaustible source of acetylene Increasing interest to the catalytic
chemistry of acetylene (see for example [1 2]) can be motivated in particular by these
considerations
Results of development of new catalytic transformations of acetylene under homo- and
heterogeneous conditions will be presented and discussed
References
1 Alonso F Beletskaya IP Yus M Chem Rev 2004 104 3079
2 Ananikov V P Beletskaya I P Organometallics 2012 31 1595
54
IL31
SYNERGISTIC EFFECTS IN DESIGNING COMBINED CATALYTIC
SYSTEMS (COMBICATrsquoS) FOR ABATEMENT OF
NITROGEN OXIDES (NOX)
AYu Stakheev
Zelinsky Institiute of Organic Chemistry Catalysis division Moscow Russia
Anthropogenic emission on nitrogen oxides (NOx = NO NO2 N2O) becomes an important issue
since the amount of anthropogenic NOx nowadays exceeds biogenic emission (~110 Mt vs 80
Mtannual) and their impact on environment is significant The most effective method for
abatement of nitrogen oxides is their selective catalytic reduction (SCR) by urea or NH3
2NO + 2NH3 + 12O2 = 2N2 + 3 H2O
However activity of the traditional NH3-SCR catalysts at the temperatures below 250oC is not
sufficient due to the stringent restrictions imposed by environmental legislations on NOx emission
from mobile sources The effective solution can be provided by Cu-containing zeolite catalyst
however high cost often limits their practical application Our recent study revealed alternative
approach and indicated that promising NH3-DeNOx activity at Treact lt 250degC CAN BE ATTAINED OVER
combined catalysts (CombiCat) comprising zeolite component (possessing high activity in SCR)
and a redox component (having high activity in NO oxidation) For such compositions we found a
pronounced synergistic effect and the catalytic activity of the COMBICATrsquoS significantly exceeds
activity of the individual components A number of compositions have been tested for searching
synergistic effects and the most remarkable results have been observed for [CuAl2O3 +FeBETA]
[MnAl2O3 + FeBETA [CeZr +FeBETA] [MnCeZr + FeBETA] MnFeBETA Interestingly that
the studied composition exhibits favorable performance in selective oxidation of NH3
2NH3 + 32 O2 = N2 + 3H2O
Therefore CombiCatrsquos are capable to accomplish two functions SCR catalyst and removal of
residual NH3 In addition to that for the compositions comprising CeO2-ZrO2 component a
promising soot oxidation activity has been observed
Detailed study of a possible origin of the observed synergistic effects suggests that the improvement
of NH3-DeNOx activity can be attributed to a ldquodual functionrdquo reaction mechanism comprising two
main stages
(1) NO + O2 harr NO2 over redox component
(2) NO + NO2 + 2NH3 rarr N2 + 3H2O over zeolite component
However further research is required for revealing overall reaction network and understanding
reaction mechanism responsible for observed synergy
55
IL32
NOVEL COLCHICINOIDS AS POTENTIAL ANTITUMOR AGENTS
A Yu Fedorov
Department of Organic Chemistry Nizhny Novgorod State University Gagarina av 23 Nizhny
Novgorod 603950 Russian Federation
A range of indole - and furane-containing allocolchicinoids was synthesized
Several from synthesized compounds manifested high in vitro and in vivo antitumor activity
Acknowledgment
We thank the Russian Foundation for Basic Research (projects 14-03-91342 and 12-03-00214-a)
The Ministry of Education and Science of The Russian Federation (project 46192014K) The
research is partly supported by the grant 02В49210003 of The Ministry of Education and
Science of the Russian Federation to Lobachevsky State University of Nizhni Novgorod
56
IL33
ENANTIOSELECTIVE CATALYSIS BY CHIRAL BROslashNSTED ACIDS AND
CHIRAL BRШNSTED BASES
M Terada
Tohoku Univsersity Department of Chemistry Sendai Japan
Chiral phosphoric acids 1 have become one of the most versatile types of chiral Broslashnsted acid
catalysts identified to date and have been applied to a broad range of enantioselective
transformations12)
In my continuing efforts to broaden the scope of enantioselective catalysis by 1
activation of oxygenated functional groups other than imines and related functional groups is our
recent research interest To expand the scope of chiral Broslashnsted acid catalysis recently a novel
chiral bis-phosphoric acid 2 was developed as a highly active and efficient enantioselective
catalyst3)
On the other hand intense interest has been devoted to the development of chiral
uncharged organosuperbase catalysts during the past decade In an effort to develop efficient chiral
organobase catalysts we designed and synthesized unique axially chiral Broslashnsted base 34)
3
functioned as the efficient enantioselective catalysts for the activation of pro-nucleophile having a
relatively acidic proton such as 13-dicarbonyl compounds To expand the scope of chiral Broslashnsted
Base catalysis development of much stronger organosuperbase is highly demanded We hence
designed a pseudo C2-symmetric bis(guanidino)iminophosphorane 4 as a novel family of chiral
organosuperbases5)
In my presentation I briefly introduce these chiral Broslashnsted acid catalysts (1
and 2) and base catalysts (3 and 4) In particular I would like to present a novel chiral Broslashnsted
base catalyst 4 in details
References
1) (a) Terada M Synthesis 2010 1929-1982 (b) Terada M Chem Commun 2008 4097-4112
2) Uraguchi D Terada M J Am Chem Soc 2004 126 5356-5357
3) Momiyama N Konno T Furiya T Iwamoto T Terada M J Am Chem Soc 2011 133
19294-19297
4) Terada M Ube H Yaguchi Y J Am Chem Soc 2006 128 1454-1455
5) Takeda T Terada M Y J Am Chem Soc 2013 135 15306-15309
57
IL34
IONIC LIQUIDS WATER AND LIQUID OR SUPERCRITICAL CO2 AS
PERSPECTIVE MEDIA FOR ASYMMETRIC ORGANOCATALYSIS
SG Zlotin
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences
Over the last decade amazing results have been associated with the extensive application of
asymmetric organocatalysts in organic synthesis In the presence of small metal-free chiral organic
molecules (α-amino acid or cinchona alkaloid derivatives BINOL phosphoric acids and other
chiral compounds) available prochiral reagents can be easily converted into chiral products of high
molecular complexity in high yields and with excellent enantioselectivities Unlike organometal
catalysts organocatalysts do not contaminate products with toxic heavy metals and this is important
in terms of medicinal chemistry However in some cases they may be responsible for hardly
separable and potentially dangerous organic impurities
To facilitate product purification and recovery of precious chiral catalysts immobilized forms of
organocatalysts tagged to polymers or ionic groups have been designed and organocatalytic
reactions have been carried out in so called ldquoneotericrdquo green solvents particularly in ionic liquids
(IL) water and liquid or supercritical (sc) carbon dioxide In these systems a catalyst and a product
are located in different phases during the catalytic process andor the working-up step
We developed highly efficient enantioselective cross-aldol reactions between various carbonyl
compounds in the presence of proline or prolinamide-derived organocatalysts in the IL andor
aqueous environment An original method for adapting -amino acid-sourced IL-supported chiral
organocatalysts to the aqueous medium via an incorporation of long-chain alkyl groups and
hydrophobic anions into their molecules and by performing asymmetric reactions in reagentswater
two-phase systems was elaborated Corresponding aldol products were obtained in high yields and
with extremely high anti -diastereo- (dr up to 98 2) and enantioselectivities (ee up to 99) under
proposed conditions After product isolation the remaining catalyst-water heterogeneous system
could be reused up to 15 times without a decrease of product yield and selectivity of the reaction1
Carbon acids in particular malonates malononitrile and anthranone appeared to react
enantioselectively with nitroalkenes in the presence of tertiary aminethiourea-derived bifunctional
organocatalyst in liquid CO2 as a green substitute of toxic organic solvents to afford the respective
Michael adducts in moderate to high yields and with enantioselectivities of up to 92 ee2 The first
ldquogreenrdquo asymmetric organocatalytic reaction in sc-CO2 namely a bifunctional squaramide-
catalyzed addition of diphenylphosphite to α-nitroalkenes to afford β-nitrophosphonates in high
yields and with ee-values of up to 94 was elaborated3 In this way the most active (R)-enantiomer
of the therapeutically useful GABAB receptor agonist baclofen a key precursor of the chiral
anticonvulsant pregabalin and both enantiomers of pharmacologically important β-amino
phosphonic acid derivatives were synthesized A significant potential of the supercritical extraction
for product isolation and catalyst recovery which completely eliminates the use of organic solvents
during the working-up procedure was demonstrated
The work was financially supported by the Russian Foundation of Basic Research (projects 12-03-
00420 14-03-31321 and 14-03-92701)
1 DE Siyutkin AS Kucherenko SG Zlotin In ldquoComprehensive Enantioselective
Organocatalysis Catalysts Reactions and Applicationsrdquo ed by PI Dalco Wiley-VCH 2013
v 2 p 617-650
2 AG Nigmatov IV Kuchurov DE Siyutkin SG Zlotin Tetrahedron Lett 2012 53 3502
3 IV Kuchurov AG Nigmatov EV Kryuchkova AA Kostenko AS Kucherenko SG
Zlotin Green Chem 2014 16 1521
58
IL35
MAKING OLEFIN METATHESIS WORK - RECENT RESULTS IN
RUTHENIUM CATALYSTS DESIGN
KL Grela
Biological and Chemical Research Centre Faculty of Chemistry University of Warsaw
Ruthenium-catalyzed olefin metathesis reactions represent an attractive and powerful
transformation for the formation of new carbon-carbon double bonds [1] This area is now quite
familiar to most chemists as numerous catalysts are available that enable a plethora of olefin
metathesis reactions [1] However formation of substituted and crowded double bonds decreasing
the amount of metal using metathesis in green context etc still remain a challenge making
industrial applications of this methodology difficult [2] These limitations can be solved by
designing new more active and stable catalysts and catalysts that can be easier removed recycled
[3]
During the lecture a number of representative examples will be presented
Artwork copy Katarzyna Felchnerowska wwwfbcomeffefineart
References
[1] Olefin Metathesis Theory and Practice Grela K (Ed) John Wiley amp Sons 2014
[2] Thayer A Chemical amp Engineering News 2007 85 (07) 37
[3] Clavier H Grela K Kirschning A Mauduit M Nolan S P Angew Chem Int Ed 2007
46 6786-6801
59
60
Oral Communications
61
62
OC1
THE FIRST CYCLOPENTADIENYL NICKEL COMPLEXES BEARING A
SILYL GROUP OR HYDROGEN SUBSTITUTED PHOSPHINE
CHELATING SIDECHAIN
I Werner H Butenschoen
Institute of Organic Chemistry Leibniz Universitaet Hannover Hannover Germany
The only known secondary phosphine pendant cyclopentadienyl complexes are those of zirconium
and hafnium reported by Ishiyama et al in 2002[1]
Since these complexes contain a reactive
phosphorus-hydrogen bond they were converted into the corresponding phosphide-substituted
cyclopentadienyl chelate complexes[2]
Both systems were successfully applied in catalytic ethylene
and styrene polymerization reactions as well as in ethylenestyrene copolymerization reactions[3]
To our knowledge no analogous complexes of late transition metals containing a phosphorus-
hydrogen or a phosphorus-silyl bond have so far been reported We report on the synthesis of the
first cyclopentadienyl nickel complexes 1-4 and 5 7 bearing a silyl group and hydrogen substituted
phosphine chelating sidechain respectively
Treatment of complex 5 with SIMes induced the decomplexation of the secondary phosphane
substituted tether delivering exclusively nickel carbene complex 6
Recrystallization of complex 7 from hexaneethyl acetate (11) at 30 degC afforded crystals suitable
for an X-ray crystal structure analysis
References
[1] T Ishiyama H Nakazawa K Miyoshi J Organomet Chem 2002 648 231
[2] T Ishiyama T Mizuta K Miyoshi H Nakazawa Organometallics 2003 22 1096
[3] T Ishiyama K Miyoshi H Nakazawa J Mol Cat A-Chem 2004 221 41
63
OC2
EXPANDED RING N-HETEROCYCLIC CARBENE TRANSITION METAL
COMPLEXES SYNTHESIS STRUCTURE APPLICATIONS IN
CATALYSIS
MS Nechaev1 AF Asachenko
2 PB Dzhevakov
2 OS Morozov
2 GV Proskurin
1 PS
Gribanov1
1 - Moscow State University Department of Chemistry Moscow Russia
2 - A V Topchiev Institute of Petrochemical Synthesis RAS Moscow Russia
N-heterocyclic carbenes (NHCs) became widely used as organocatalysts and as ligands in transition
metal catalysis Most of NHC-metal complexes known to date are derived from five-membered ring
imidazol-2-ylidene and imidazolin-2-ylidene type carbenes In recent years our group develops
chemistry of 6- 7- and 8-membered ring carbenes Expanded ring carbenes (er-NHCs) exhibit
superior stereoelectronic properties in comparison with five-membered ring counterparts
Expansion of the ring leads to significant increase in donor strength and sterical hindrance
In this contribution we report our recent results on theoretical calculations of electronic structure
and ligand properties of er-NHCs efficient methods of synthesis of precursors and generation of
free carbenes synthesis of late transition metal (Cu Ag Au Pd) complexes It was found that er-
NHC complexes of palladium are highly active in Suzuki-Miyaura coupling in water and
dimerization of terminal alkynes with formation of E-enynes Cationic gold complexes are active
catalysts of addition of nucleophiles to carbon-carbon triple bonds
64
OC3
PALLADIUM-CATALYZED CndashH ALKENYLATION OF ARENES USING
SULFUR-CONTAINING DIRECTING GROUPS A COMPARATIVE STUDY
KV Luzyanin AN Marjanov VP Ananikov
Laboratory of Cluster Catalysis Saint Petersburg State University Universitetsky pr 26 Stary
Petergof 198504 Russia
Direct alkenylation of organic substrates via directing-group assisted functionalization of the CH
bond has emerged as a valuable tool for creation of new sp2-sp
2 bonds In the contrast to the
MirozokindashHeck reaction that starts from the aryl halides this procedure works with inactivated
arenes and is favorable from both economical and environmental points of view Several types of
directing groups have been evaluated in the direct alkenylation up to date eg ketones and
carboxylates amides pyridine sulfoxides and ethers and thioethers Among them functionalization
of sulfur-containing compounds (Scheme 1) ie pyridine thioesters and sulfoxides as well as
structurally related benzylic thioethers (in those sulfur moiety plays a role of a directing group)
attracts rapidly growing attention On the one hand functionalization of such compounds leads to
interesting derivatives containing both alkene and sulfur functions while on the other hand sulfur-
based directing groups in these species can be easily removed after reaction from the resulting
products without compromising other functionalities1ndash3
Scheme 1 Direct alkenylation of arenes using sulfur-containing directing groups
In the current report we summarize data accumulated up to date regarding direct CH-alkenylation
of sulfur-containing organic compounds A particular emphasis is given to the evaluation of the
assistance provided by different sulfur-containing directing groups in comparison to other common
directing moieties known to be employed for this purpose
Acknowledgements This work has been partially supported by the Saint Petersburg State
University (research grant from Laboratory of Cluster Catalysis) and the Russian Fund for Basic
Research (grant 14-03-01005)
References 1 Garciacutea-Rubia A Fernaacutendez-Ibaacutenez M A Goacutemez Arrayaacutes R Carretero J C Chem Eur J
2011 17 3567ndash3570
2 Yu M Xie Y Xie C Zhang Y Org Lett 2012 14 2164ndash2167
3 Zhang X-S Zhu Q-L Zhang Y-F Li Y-B Shi Z-J Chem Eur J 2013 19 11898ndash
11903
65
OC4
IN PURSUIT OF A NOVEL IMIDATE-BASED SALEN-TYPE LIGAND
CLASS
J Van Der Eycken1 P Janssens
1 T Noel
2
1 - Ghent University Department of Organic Chemistry
2 - Eindhoven University of Technology Department of Chemistry and Chemical Engineering
Micro Flow Chemistry amp Process Technology
An increasing ecological awareness and global competitiveness have challenged the chemical
industry towards a higher level of sustainability through innovation and technology In research the
majority of topics on sustainable process development deals with catalysis[1]
Furthermore in
organic synthesis transition metal catalysis already plays a vital role in the synthesis of biologically
active compounds[2]
N N
OH HO
N N
H H H HO O
OH HO
L1 L2
Bisimidate ligand L2 shows striking similarities with Salen ligands (L1) We reasoned that this
could open new opportunities for our already well-established imidate ligand family [3-5]
Nevertheless the applicability of this ligand in the MnV-catalyzed asymmetric epoxidation reaction
turned out to be more complicated than expected
In this communication the search towards an effective novel imidate-based Salen-type ligand class
will be discussed from a ligand design point of view
References
[1] Dichiarante V Ravelli D Albini A Green Chem Lett Rev 2010 3 105
[2] a) Noyori R Angew Chem Int Ed 2002 41 2008 b) Busacca CA Fandrick DR Song
JJ Senanayake CH Adv Synth Catal 2011 353 1825
[3] a) Noeumll T Bert K Van der Eycken E Van der Eycken J Eur J Org Chem 2010 21
4056 b) Bert K Noeumll T Van der Eycken J Org Biomol Chem 2012 10 8539 c) Noeumll T
Bert K Janssens P and Van der Eycken J (2012) ldquoChiral Imidate Ligands Synthesis and
Applications in Asymmetric Catalysisrdquo in Innovative Catalysis in Organic Synthesis
Oxidation Hydrogenation and C-X Bond Forming Reactions (ed P G Andersson) Wiley-
VCH Verlag GmbH amp Co KGaA Weinheim Germany doi 1010029783527646586ch14
66
OC5
NITROALKANES IN PPA AS NEW REAGENTS FOR DIRECT METAL-
FREE AMINATION OF ARENES
AV Aksenov1 NA Aksenov
1 IV Aksenova
1 M Rubin
2 DA Aksenov
1
1 - Department of Chemistry North Caucasus Federal University Stavropol Russian Federation
2 - Department of Chemistry University of KansasLawrence USA
Aromatic amines represent an important class of organic compounds Many of them demonstrate
important biological activities Various multi-step methods for preparation of these compounds
have been developed including electrophilic nitrationreduction sequence Schmidt and Beckmann
rearrangements etc The most appealing methods however are those that allow for direct
introduction of an amino-group to a non-substituted arene over a single step
Direct electrophilic acetamidation of arenes 2 with primary nitroalkanes 1 in polyphosphoric acid
(PPA) recently developed in our laboratories can be viewed as an example of such an approach
R
N+
O
O
P P A
R
N+
O
O P
O
O H
O R
2
R3
R1
R4
R2
N
R
O
PO
O H
O
R3
R4
R1
R2
NH
R
OR3
R1
R4
6 3 -9 2
2
1
3 R=Me Pr Ph Bn R
1 R
2 R
3 R
4=H Me OH MeO CHO
Benzene and arenes with electron-donating substituents can be engaged in this reaction Electron
deficient arenes are inert The process is highly selective the electrophilic attack is always directed
to para-position with respect to a substituent already present in the ring
Anthracene 4 and indole 5 were successfully involved into the acetamidation reaction In reaction of
dibenzo-18-crown-6 ether monoacetamide was formed along with quite a large amount of bis-
acetamination isomeric products
The reaction involving secondary nitroalkanes is also interesting Since the nitroso compound 4
resulting from electrophilic attack to the aromatic ring is not able to isomerize oxime it attacks a
second molecule of arene After rearrangement this leads to the formation of diarylamines 5
N+ O
O P O2H
- H +N
O H
O P O2H
R1
R2
P P A
O
R1
R2
NO
R1
R2
- H2O R
1
R2
N
O HR
1
R2
R1
R2
R1
R2
N
O H
R1
R2
R1
R2
NH
+-P P A
+
4
5 5 5 -6 1 R
1 R
2 =H Me MeO CHO
A novel protocol for direct and regioselective metal-free acetamination and amination of arenes in
reactions with primary and secondary nitroalkanes in polyphosphoric acid media was developed A
new preparative approach to 5-aminoindoles and diarylamines employing this reaction was
demonstrated
This work was carried out with financial support from the Russian Foundation Basic Research
(grants 13-03-00304 a and 14-03-31288 mol_a)
67
OC6
UROTROPINE ISOMER (14610-TETRAAZAADAMANTANE)
MOLECULAR SIMPLICITY AND MOLECULAR COMPLEXITY OF
HETEROADAMANTANE CAGE
AYu Sukhorukov AN Semakin IS Golovanov SL Ioffe VA Tartakovsky
ND Zelinsky Institute of Organic Chemistry Moscow Russia
For more than 100 years heteroadamantanes have been objects of rapt attention for fundamental
and applied chemistry These cage polycyclic systems represent interest not only due to their unique
properties but also as convenient models for the study of basic problems dealing with structure and
reactivity of organic compounds Among many heteroadamantanes 1357-tetraazaadamantane
(urotropine) which was first obtained by A Butlerow in 1859 plays probably the most important
role from an applied point of view Urotropine is widely used in medicine polymer production
food industry as well as organic synthesis coordination chemistry and MOFs design This simplest
Td-symmetrical 1357-tetraazaadamantane is the only known representative of the class of
tetraazaadamantanes In this context the possibility of existence of other tetraazaadamantanes
isomeric to urotropine represents considerable fundamental interest
The present report deals with the first synthesis of 14610-tetraazaadamantane (ldquoisourotropinerdquo)
the C3v-symmetrical structural isomer of urotropine and a series of its derivatives (see Figure) X-
Ray and quantum-chemical studies demonstrate remarkable distinctions in structures of urotropine
and ldquoisourotropinerdquo cages probably arising from different types of lp(Neq) C N interactions in
these heterocage systems Since substitution at bridge and bridgehead nitrogen atoms can be easily
installed 14610-tetraazaadamantane can be considered as a new rigid multivalent (3+1) scaffold
for the design of complex functional molecules and materials
Acknowledgement
The financial support from RFBR (grant 14-03-00933a) and Russian Presidentrsquos Council for Grants
(grant MK-391820133) is greatly acknowledged
68
OC7
PALLADIUM-CATALYZED CROSS-COUPLING REACTION OF
ALCOHOL WITH ARYL CHLORIDE THROUGH C-C BOND ACTIVATION
C-H Jun H-S Park D-S Kim
Yonsei University Department of Chemistry Seoul South Korea
The C-C bond activation is one of challenging subjects in organometallic chemistry1 Especially
catalytic version of C-C bond activation has been recently achieved by chelation assisted transition
metal catalyst consisted of Rh(I) and 2-amino-3-picoline2 During the course of our studies on
these types of C-C bond activation we found decarbonylative esterification of aliphatic alcohol
with aryl chloride by palladium metal as shown below For example when the reaction of
chlorobenzene and 1-naphtylethanol was carried out at 150oC under PdC and NaF base a mixture
of three products 1-naphtylethyl benzoate ester benzene and 1-methylnaphthalene was obtained
in reasonable yields
The reaction mechanism is proposed as follows The reaction proceeds through several consecutive
reactions Initially primary alcohol is oxidized by aryl chloride to aldehyde with formation of aryl-
H under palladium catalyst Aldehyde is decarbonylated by Pd to generate alkane and (CO)Pd The
intermediate (CO)Pd is oxidatively added to aryl chloride to form acyl-PdCl complex which reacts
with alcohol to give ester compounds In this reaction reactivity of substrate should be well
balanced The reactivity of chloroarene is suited for this purpose since other aryl halide such as
bromobenzene and iodobenzene did not show any reactivity in this reaction This result is quite
interesting since aryl chloride is least reactive for common C-C bond coupling reaction while aryl
iodide is very reactive The reaction works well with aryl chloride One of merits in this protocol is
that carbonylation proceeds without using toxic CO gas and CO source is non-toxic alcohol More
detailed mechanistic studies using 13
C-enriched or deuterated alcohol will be discussed
References
1 Jun C -H Chem Soc Rev 2004 33 610-618
2 Park Y J Park J -W Jun C -H Acc Chem Res 2008 41 222-234
69
OC8
RADICAL-CATIONS OF ACETYLENE COMPOUNDS IN CARBON-
CARBON BOND FORMING REACTIONS
AV Vasilyev
Saint Petersburg State Forest Technical University Institutsky per 5 Saint Petersburg 194021
Russia Saint Petersburg State University Institute of Chemistry
Radical-cations of acetylene compounds A generated under oxidation of alkynes I in systems
PbO2-strong acid (CF3CO2H HF HSO3F) are key reaction intermediates in various new carbon-
carbon bond forming processes [1-6]
Depending on structure the species A lead to formation of a variety of products II-VII When
substituents X are moderate electron acceptors CO2R COAr COR PO(OEt)2 trans-ethenes II are
stereoselectively formed In case of stronger acceptors furan derivatives III (X = COCF3
СОCO2Et) or diketones IV (X = CF3) are formed
In different acidic systems radical-cations of diarylacetylenes (X = Ar) give unsaturated diketones
V (in CF3CO2H) butadiene difluiorides VI (in HF) or dichlorides VII (in HSO3F followed by
quenching in HClaquaconc) The last ones are electro-cyclically converted into naphthalenes VIII
C
C C
C
Ar Ar
FF
Ar Ar
C C
Ar
C C
Ar
Cl Cl
Ar Ar
CC
C
O O
C
Ar Ar
ArAr
Cl
Ar
Ar
Ar
R
H+ = CF3CO2H
H+ = HF
1 H+=HSO3F 2 HCl
VI
VIII
X = COCF3
COCO2EtC
OX
C C
C
OC
Ar
Ar Y
C
OX
C C
C
OX
Ar
ArX = CO2Alk
COAr COMe
PO(OEt)2
C C X
C CAr
I
A
III
II-e
Ar
X
PbO2H+
CF3F3C
C C
C
O O
C ArArHH
X = CF3
Y = CF3 CO2Et
X = Ar
IVV
X = Ar
X = Ar
VII
[1] Vasilyev AV Rudenko AP Russ J Org Chem (in Engl) 1997 V33 P 1555-1584
[2] Shchukin AO Vasilyev AV Fukin GK Rudenko AP Russ J Org Chem (in Engl)
2007 V43 P1446-1450
[3] Vasilyev AV Aristov SA Fukin GK Kozhanov KA Bubnov MP Cherkasov VK Russ
J Org Chem (in Engl) 2008 V44 P 791-802
[4] Vasilyev AV Shchukin AO Walspurger S Sommer J Eur J Org Chem 2008 4632
[5] Vasilyev AV Rudenko AP Russ J Org Chem (in Engl) 2010 V46 P1282-1289
[6] Alkhafaji HMH Vasilyev AV Ryabukhin DS Rudenko AP Muzalevskiy VM
Nenajdenko VG Russ J Org Chem (in Engl) 2013 V49 P 621-623
70
OC9
ACTIVATION OF Ru-BASED OLEFIN METATHESIS CATALYSTS
A Poater1 L Cavallo
2
1 - Institut de Quimica Computacional i Catаlisi and Departament de Quimica Universitat de
Girona Campus de Montilivi E-17071 Girona Catalonia Spain
2 - Kaust Catalysis Center Physical Sciences and Engineering Division King Abdullah University
of Science and Technology Thuwal 23955-6900 Saudi Arabia
In recent years olefin metathesis catalyzed by N-heterocyclic carbene ruthenium complexes has
attracted remarkable attention as a versatile tool to form new C=C bonds[1] The last developed
(pre)catalysts show excellent performances and this achievement has been possible because of
continuous experimental and computational efforts to understand the laws controlling the behavior
of these systems This perspective talk rapidly traces the ideas and discoveries that computational
chemistry contributed to the development of these catalysts with particular emphasis on catalysts
presenting a N-heterocyclic carbene ligand Specifically one of the most important challenges in
ruthenium-catalyzed olefin metathesis is to increase the stability of the catalysts under reaction
conditions and this hopefully without loss of activity Special interest has been addressed to study
the activation of the second-generation Grubbs catalysts which has clarifier either a dissociative or
an interchange mechanism is feasible[2]
Although in the solid state most ruthenium-based olefin metathesis catalysts are stable to oxygen
and moisture in solution decomposition usually occurs readily Understanding the decomposition
routes of catalysts is extremely important as any insight gained in this area can guide catalyst design
efforts to participate then in the synthesis of drugs[34] Furthermore new challenging projects
plan to modify the structure of the NHC ligands or replace this ligand by alkylidene ligands and
even the substitution of the metal is a goal moving to more environmentally friendly metals
[1] G C Vougioukalakis R H Grubbs Chem Rev 110 1746 (2010)
[2] C A Urbina-Blanco A Poater T Lebl S Manzini A M Z Slawin L Cavallo S P Nolan
J Am Chem Soc 135 7073 (2013)
[3] S Manzini C A Urbina-Blanco A Poater A M Z Slawin L Cavallo S P Nolan Angew
Chem Int Ed 51 1042 (2012)
[4] S Manzini A Poater D J Nelson L Cavallo S P Nolan Chem Sci 5 180 (2014)
71
OC10
CHEMICAL REACTIVITY IN PROTEINS AND WATER QMMM MD
INSIGHTS INTO EFFECTS OF LOCAL STRUCTURAL ENVIRONMENTS
ON BOND CLEAVAGE
Y Zhao BJ Wang RB Wu ZX Cao
Department of Chemistry Xiamen University Xiamen 361005 China
Water and proteins play a quite important role in chemical and biological processes In past few
years we carried out a systematic investigation on the effect of local structural environments on
reactivity towards hydrolysis C-N C-O and C-H bond cleavages in proteins and water Using
Born-Oppenheimer ab initio QMMM MD simulations a state-of-the-art approach to simulating
enzymes we have investigated the structural features of zinc enzymes nucleoside hydrolase and
deaminase and plausible enzymatic mechanisms The molecular complexity of active domain in
enzyme and roles of conserved residues and protein environments in enzymatic catalysis have been
explored In particular the different coordination modes and fast ligand exchanges of zinc
coordination has been suggested to be one key catalytic feature of the zinc ion and the chelation
mode of hydroxamate with the zinc ion in HDACs is modulated by water access to the linker
binding channel This new insight into the interplay between the linker binding and the zinc
chelation emphasizes its importance for the development of new class-IIa-specific HDAC
inhibitors Our calculations indicate that the reliable theoretical treatment on the water-mediated
proton transfer and most hydrolysis reactions of carbonyl compounds such as aldehydes ketones
esters amides the carboxylic acids and their derivatives requires use of the large basis set and
suitable cluster-continuum model The effects of solvent and structural modification on hydration
and hydrolysis of carbonyl compounds have been discussed
Acknowledgements This work was supported by the National Science Foundation of China
(21133007 and 21373164) and the Ministry of Science and Technology (2011CB808504)
References
1 N Chen H Ge J Xu Z Cao and R Wu Biochim Biophys Acta 2013 1834 1117
2 R Wu W Gong T Liu Y Zhang and Z Cao J Phys Chem B 2012 116 1984
3 B Wang and Z Cao Chem Eur J 2011 17 11929
4 B Wang and Z Cao Angew Chem Int Ed 2011 50 3266
5 R Wu Z Lu Z Cao and Y Zhang J Am Chem Soc 2011 133 6110
6 Y Zhao N Chen R Wu and Z Cao 2013 submitted
72
OC11
MECHANISM OF INTRAMOLECULAR HECK REACTION BY DENSITY
FUNCTIONAL THEORY
A Ayyappan D Yogeswara Rao
Indian Institute of Technology Kharagpur Department of Chemistry West Bengal 721392 India
Heck Reaction the palladium-catalyzed C-C coupling between aryl halides or vinyl halides and
activated alkenes in the presence of a base is widely used in syntheric chemistry Intramolecular
version of Heck reaction is a route to the generation carbocycles that are scaffolds of many
important natural products and biologically active molecules Although the mechanism of
intermoelcular Heck reactions is well established the intramelecular variant is not analyzed in detail
for its mechanistic features Using Density Functional Theory computations we have explored the
the catalytic cycle of intramolecular Heck reaction that involves oxidative addition migratory
insertion (cyclization) and β-hydride elimination (See Figure) Two pathways were analyzed which
differ in their initial coordination face (Re or Si) of the terminal alkene with the metal centre The
choice of pathway is not evident from free energy profile because one of the pathways have higher
barrier for oxidative addition the other requires high activation energy for β-hydride elimination
Detailed analysis of the mechanism will be presented In addition our attempts to analyze such
complex reaction mechanisms by kinetic simulations will be discussed
Figure Catalytic cycle for the intramolecular Heck reaction
73
OC12
CYCLODIMERIZATIONS OF DONOR-ACCEPTOR CYCLOPROPANES
SHORTCUT APPROACH TO COMPLEX RING SYSTEMS
EM Budynina OA Ivanova AO Chagarovskiy IV Trushkov
Moscow State University Department of Chemistry Moscow Russia
Cyclodimerization is among the most challenging and fascinating reactions providing significant
increase in structural complexity within one operation step in highly stereoselective manner and
occurring both in vivo and in vitro In organic synthesis among typical substrates that undergo
cyclodimerizations donor-acceptor (DA) cyclopropanes1 in which small ring is vicinally activated
with donor and acceptor groups occupy a special place Currently at least dozen types of Lewis
acid-triggered cyclodimerization of such DA cyclopropanes as 2-(het)aryl-cyclopropane-11-
diesters are known which open rapid approaches to diverse ring compounds including complex
polycyclic and bridged molecular systems2
Recently on basis of (3+3)-cyclodimerizations of 2-arylcyclopropane-11-diesters we developed
straightforward and efficient approaches to 14-diarylcyclohexanes 1-aryltetralins or 910-
dihydroanthracenes2a
(3+2)-Cyclodimerizations of similar cyclopropanes provide an easy access to
diarylcyclopentanes2bc
and arylindanes2d
Cyclodimerizations of 3- and 4-indolyl-derived DA
cyclopropanes allows for the construction of complex tetra- and heptacyclic cores of bisindoles2e
1 a) Reissig H-U Zimmer R Chem Rev 2003 103 1151 b) De Simone F Waser J
Synthesis 2009 3353 c) Melrsquonikov MYa Budynina EM Ivanova OA Trushkov IV
Mendeleev Commun 2011 21 293 d) Schneider TS Kaschel J Werz DB Ang Chem Int
Ed 2014 53 101002anie201309886
2 a) Ivanova OA Budynina EM Chagarovskiy AO Trushkov IV Melnikov MYa J
Org Chem 2011 76 8852 b) Chagarovskiy AO Ivanova OA Budynina EM Trushkov
IV Melnikov MYa Tetrahedron Lett 2011 52 4421 c) Novikov RA Korolev VA
Timofeev VP Tomilov YuV Tetrahedron Lett 2011 39 4996 d) Ivanova OA Budynina
EM Skvortsov DA Limoge M Bakin AV Chagarovskiy AO Trushkov IV
Melnikov MYa Chem Commun 2013 49 11482 e) Ivanova OA Budynina EM
Chagarovskiy AO Rakhmankulov ER Trushkov IV Semeykin AV Shimanovskii NL
Melnikov MYa Chem Eur J 2011 17 11738 f) Novikov RA Tarasova AV Korolev
VA Timofeev VP Tomilov YuV Ang Chem Int Ed 2014 53 3187 g) Novikov RA
Tomilov YuV Helv Chim Acta 2013 96 2068
74
OC13
USING RING STRAIN RELEASE FOR ALLEVIATION OF
TRANSANNULAR STRAIN SMALL RING-TEMPLATED SYNTHESIS OF
MEDIUM HETEROCYCLES
M Rubin M Rubina A Edwards P Ryabchuk
University of Kansas Department of Chemistry
A highly efficient diastereocenvergent reaction of bromocyclopropanes with various nucleophiles
have been recently developed in our laboratories1-7
This reaction involves a base-assisted
dehydrohalogenation to produce a highly reactive cyclopropene intermediate which undergoes
subsequent nucleophilic addition across the strained C=C bond Different intramolecular modes of
this reaction will be presented Possibilities for assembly of heterocyclic scaffolds with various ring
sizes including enantiomerically pure medium heterocycles will be demonstrated The mechanistic
aspect of this transformation and the means of controlling its diastereoselectivity will be discussed
Br
Nu
R
O
N O HN
O
R
R
Me
O
BaseTHF
18-crown-6 (cat)
t-BuOKTHFKOHTHF
t-BuOK DMSO
Ar Me
O
N
R
O
H
H
8-membered 7-10-membered
8-9-membered
N
Ph
Ph
O
t-BuOK THF
5-membered
O
O
R
R8-membered
O
O
O
Me
NH
HNO
Me
15-memberedt-BuOK DMSO
t-BuOK THF
References
[1] Alnasleh B K Sherrill W M Rubina M Banning J Rubin M J Am Chem Soc 2009
131 6906-6907
[2] Banning J E Prosser A R Rubin M Org Lett 2010 12 1488-1491
[3] Prosser A R Banning J E Rubina M Rubin M Org Lett 2010 12 3968-3971
[4] Banning J E Prosser A R Alnasleh B K Smarker J Rubina M Rubin M J Org
Chem 2011 76 3968-3986
[5] Ryabchuk P Rubina M Xu J Rubin M Org Lett 2012 14 1752-1755
[6] Banning J E Gentillon J Ryabchuk P Prosser A R Rogers A Edwards A Holtzen
A Babkov I A Rubina M Rubin M J Org Chem 2013 78 7601-7616
[7] Ryabchuk P Edwards A Gerasimchuk N Rubina M Rubin M Org Lett 2013 15
6010-6013
75
OC14
THE STRATEGY FOR ATOM ECONOMICAL REDUCTIVE ADDITION
DEOXYGENATION
D Chusov PN Kolesnikov VI Maleev NZ Yagafarov
ANNesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences
Herein we present the concept of using carbon monoxide for atom economical reductive addition
deoxygenation without external hydrogen source [1] We are utilizing this idea by showing that N-
H and C-H bonds of the reagents could be used as hydrogen source (Fig 1)
Figure 1
References
D Chusov B List Angew Chem Int Ed 2014 53 DOI 101002anie201400059
76
OC15
DINUCLEAR CATALYSIS ACCELERATED METAL-DEPENDENT RING-
OPENING POLYMERIZATION OF LACTIDE
E Kirillov
Universite de Rennes 1 UMR 6226 - CNRS 35042 Rennes France
Multinuclear olefin polymerization catalysts (incorporating several active metal centers in one and
the same molecule) have recently emerged as a distinct and brand new class of molecular catalysts 1
Implicit cooperative behavior2 of two or more metal centers in active species of these systems can
contribute to enhanced performance (with respect to mononuclear analogues) in terms of activity
chain-transfer kinetics and also monomers selectivity in copolymerization reactions
Dinuclear complexes of aluminum and indium with a bis(phenoxy-imine) platform have been
synthesized and used in the polymerization of lactide3a
Kinetic studies demonstrated that the
dialuminum precursor (Scheme 1) provides a more favorable reaction pathway in terms of
activation free energy than that of directly related monoaluminum systems3b
No similar trend was
observed with the corresponding diindium monoindium systems which was attributed to a
dissimilar ROP mechanism Details of the mechanisms and key factors of the dinuclear catalysis
will be discussed
Scheme 1 A dinuclear aluminum system enables a 5-to-10 fold boost in activity when compared to
its monoaluminum analogues
1 Delferro M Marks T J Chem Rev 2011 111 2450
2 Bratko I Goacutemez M Dalton Trans 2013 42 10664
3 (a) Normand M Roisnel T Carpentier J-F Kirillov E Chem Commun 2013 49 11692
(b) Normand M Dorcet V Kirillov E Carpentier J-F Organometallics 2013 32 1694
77
OC16
RECENT METHODOLOGICAL DEVELOPMENTS FOR THE QUANTUM
CHEMICAL STUDY OF COMPLEX SYSTEMS
S Irle
Nagoya University Department of Chemistry Nagoya Japan
The structural complexity of molecular clusters increases with size due to the associated rapidly
growing configuration space Two examples are realized in i) the transition from molecular to bulk
systems and ii) in the simulation of extended biosystems In such systems traditional quantum
chemical approaches of investigations are hampered by the vastly increasing computational cost
even considering ever-growing supercomputer capabilities Computationally inexpensive yet
accurate schemes such as the density-functional tight-binding (DFTB) method [1] and there linear
scaling versions promise here a significant advantage
We have recently engaged in developing novel methodologies for systems with increasing
structural complexity driven by motivation from experimental studies In this presentation we will
review a) the Kick-fragment-based ldquoKick3rdquo conformationally aware approach for studying
molecular [2] and ionic liquid clusters with increasing size and our implementation of the fragment
molecular orbital (FMO) method [3] with DFTB called ldquoFMO-DFTBrdquo in the popular GAMESS-
US quantum chemistry package [4] The computational effort of the method scales nearly linearly
with system size with a negligible pre-factor and allows the efficient massively-parallel quantum
chemical geometry optimization and direct molecular dynamics (MD) simulations of systems
containing several tens of thousands of atoms in particular when fragments consist of units with
less than 50 atoms [5] The method should be particularly useful to predict structures of new
artificial peptides and proteins predict enzymatic reaction pathways estimate free energy
contributions along pathways where large parts or even the entire protein including surrounding
water is treated quantum chemically and to simulate the effects of highly polarizable andor
charged solvents in explicit-solvent MD simulations
Unlike other linear scaling schemes such as divide and conquer approaches (DC) FMO-DFTBs
very design allows the insightful decomposition of interaction energies between ligands and
proteins in terms of electrostatics exchange-repulsion charge transfer dispersion and solvent
screening contributions in a straightforward manner
[1] M Gaus Q Cui M Elstner J Chem Theory Comput 7 931 (2011)
[2] M A Addicoat S Fukuoka A J Page S Irle J Comput Chem 34 2591 (2013)
[3] D G Fedorov T Nagata K Kitaura Phys Chem Chem Phys 14 7562 (2012)
[4] M W Schmidt K K Baldridge J A Boatz S T Elbert M S Gordon J H Jensen S
Koseki N Matsunaga K A Nguyen S Su T L Windus M Dupuis and J A Montgomery
Jr J Comput Chem 1993 14 1347 httpwwwmsgameslabgovgamessindexhtml
[5] Y Nishimoto D G Fedorov S Irle submitted
78
OC17
QUANTUM CHEMICAL MODELING IN STUDIES OF MOLECULAR
MECHANISMS OF ENZYME CATALYSIS
AV Nemukhin
Chemistry Department MV Lomonosov Moscow State University Moscow 199991 Russia NM
Emanuel Institute of Biochemical Physics Russian Academy of Sciences Moscow Russia
Recent results [1-3] of modeling chemical transformations in enzyme active sites using quantum-
based approaches will be discussed We apply quantum mechanicsmolecular mechanics (QMMM)
approaches to compute minimum energy pathways connecting enzyme-substrate and enzyme-
product complexes Appropriate crystal structures from the Protein Data Bank usually serve as a
source of coordinates of heavy atoms to create molecular model systems After in silico
construction of a three-dimensional full-atom model evolution of the model system along carefully
selected reaction coordinates is analyzed
Several examples of such modeling will be presented The complete cycle of chemical
transformations in penicillin acylase a unique enzyme that belongs to the recently discovered
superfamily of N-terminal nucleophile hydrolases with its most specific substrate penicillin G
leading to formation of 6-aminopenicillanic and phenylacetic acids [1] will be presented Keton-
ketal transformations at the active site of matrix metalloproteinases characterized computationally
[2] may be explored to propose specific inhibitors Chemical reactions in photoreceptor proteins
constitute an active field of application of QMMM modeling the case of BLUF domains will be
discussed [3]
Simulation results of guanosine triphposphate hydrolysis (GTP) by small GTPases icluding Ras
protein will be in focus According to newly obtained data the molecular events of the chemical
steps upon GTP hydrolysis include (i) cleavage of the phosphorus (Pγ) -oxygen bond in GTP upon
approach of the properly aligned catalytic water molecule producing GDP (ii) formation of a new
chemical bond between phosphorus and oxygen of water (iii) redistribution of protons between
reacting species leading to inorganic phosphate Pi
References
[1] Grigorenko BL Khrenova MG Nilov DK Nemukhin AV Švedas VK Catalytic Cycle of
Penicillin Acylase from Escherichia coli QMMM Modeling of Chemical Transformations in
the Enzyme Active Site upon Penicillin G Hydrolysis ACS Catal 2014 V 4 P 2521ndash2529
[2] Khrenova MG Nemukhin AV Savitsky AP Computational Characterization of Ketone-
Ketal Transformations at the Active Site of Matrix Metalloproteinases J Phys Chem B 2014
V 118 P 4345-4350
[3] Khrenova MG Nemukhin AV Domratcheva T Photoinduced Electron Transfer Facilitates
Tautomerization of the Conserved Signaling Glutamine Side Chain in BLUF Protein Light
Sensors J Phys Chem B 2013 V 117 P 2369-2377
79
OC18
EXCITED STATES AND MOLECULAR INTERACTIONS IN PROTEINS
AND SOLUTIONS
JH Hasegawa
Catalysis Research Center Hokkaido University Sapporo Japan
Solvatochromism and fluorescent solvatochromism are well-known phenomena and there are rich
accumulations in experimental publications Color tuning in proteins such as human color vision
and fluorescent proteins could be also classified to solvatochromism but with a specific
environment where anisotropic molecular interactions play important roles
We have studied biological color tuning with the SAC-CIMM calculations in which MM
description was adopted for the environmental effect This classical description for the environment
works very well for explaining the color tuning mechanisms
In some cases however environmental electronic structure effect becomes important To
investigate the origin of the QM effect we propose a scheme based on the wave function theory
with a MO localization scheme The role of the environmental electronic effect was analyzed in
terms of amino acidsrsquo orbital delocalizations excitonic interactions excited-state polarization and
dispersion interactions In the presentation we would show some results of pilot applications
80
OC19
CATIONIC GOLD-CATALYZED HETEROANNULATIONS
EV Van Der Eycken
University of Leuven (KU Leuven) Department of Chemistry Leuven Belgium
Gold catalysis is one of the fast growing research topics of modern organic chemistry In this
context gold-catalyzed carbocyclization and heteroannulation strategies have recently attracted
much attention due to the selective and efficient activation of the C-C triple bond towards a wide
range of nucleophiles Moreover the combination of multicomponent reactions with gold catalysis
gives access to complex molecular architectures in few steps as compared to traditional multistep
processes We will comment on our recent findings in this field A concise route to indoloazocines1
via a sequential Ugigold-catalyzed intramolecular hydroarylation2 will be presented A diversity-
oriented approach to spiroindoles via a post-Ugi gold-catalyzed diastereoselective domino
cyclization3 will be described (Scheme) as well as a regioselective approach for the synthesis of
pyrrolopyridinones and pyrroloazepinones employing a gold(I)platinum(II) switch4
N
O R3
H2N
R4
COOHR5
NC+
i) Ugi-4CR
NN
N
R5
O
O R3
(+-)
H
R1
R2
R2
R4
R1ii) cationic gold rt
13 examplesup to 80 yield
References
1 Synthesis of Azocino[54-b]indoles via Au-Catalyzed Intramolecular Alkyne Hydroarylation V
A Peshkov O P Pereshivko E V Van der Eycken Adv Synth Cat 354 2841-2848 2012
2 Concise route to indoloazocines via a sequential Ugigold-catalyzed intramolecular
hydroarylation S G Modha D D Vachhani J Jacobs L Van Meervelt E V Van der
Eycken Chem Commun 48 (52) 6550ndash6552 2012
3 Diversity-Oriented Approach to Spiroindolines Post-Ugi Gold-Catalyzed Diastereoselective
Domino Cyclization S G Modha A Kumar D D Vachhani J Jacobs S K Sharma V S
Parmar L Van Meervelt E V Van der Eycken Angew Chem Int Ed 51 9572-9575 2012
4 Gold(I) and Platinum(II) switch A post-Ugi intramolecular hydroarylation to pyrrolopyridinones
and pyrroloazepinones S G Modha A Kumar D D Vachhani S K Sharma V S Parmar E
V Van der Eycken Chem Comm 48 10916-10918 2012
81
OC20
Pd-SUPPORTED BIMETALLIC COMPOSITIONS FOR
STEREOSELECTIVE LIQUID PHASE SEMI-HYDROGENATION OF
DIPHENYLACETYLENE
IS Mashkovsky1 AV Sergeeva
1 OV Turova
1 MN Vargaftik
2 NYu Kozitsyna
2 AYu
Stakheev1
1 - Zelinsky Institute of Organic Chemistry RAS Moscow Russia
2 - Kurnakov Institute of General and Inorganic Chemistry RAS Moscow Russia
This study was focused on the development of the efficient catalyst for selective semi-
hydrogenation of internal alkene Diphenylacetylene (DPA) was used as a model compound The
catalytic compositions based on Pd-Zn Pd-Co Pd-Ni were investigated The samples were
prepared via two techniques (1) on the basis of palladium acetate heterobimetallic complexes as
precursors and (2) using traditional co-impregnation by individual metal salts It was found that the
systems based on bimetallic acetate complexes exhibited a substantial increase in selectivity to
alkene and cis-isomer formation at high conversion of the parent alkyne (DPA) albeit at the
expense of some decrease in the activity The detailed physicochemical study with TEM-EDS
SEM-EDS EXAFS and IR-spectroscopy reveals that the use of heterobimetallic acetate complex as
a precursor allows us to avoid metallic phase segregation during the reduction treatment of the
catalyst which ensures high homogeneity of bimetallic particles and leads to enhanced selectivity
Financial support was provided by RFBR foundation grants 12-03-31487 13-03-12176
Рис 1 Dependency of selectivity to cis-isomer and alkene on DPA conversion for PdAl2O3
catalyst modified with Co Zn and Ni in liquid phase DPA hydrogenation
Se
lecti
vit
y t
o c
is-i
so
me
r
0
10
20
30
40
50
60
70
80
90
100
70 80 90 100
0
10
20
30
40
50
60
70
80
90
100
70 80 90 100
DPA conversion
093PdAl2O3
093Pd-052ZnAl2O3
093Pd-053NiAl2O3
093Pd-053CoAl2O3
DPA conversion
Se
lecti
vit
y t
o a
lke
ne
H
H
H
H
H
H
+
H
H
H
H
+
093PdAl2O3
093Pd-052ZnAl2O3
093Pd-053NiAl2O3
093Pd-053CoAl2O3
82
OC21
DESIGN OF NANOSTRUCTURES ON THE BASIS OF TWO
PHARMACOPHORIC FRAGMENTS - FULLERENE AND PIPERIDINE
DERIVATIVES
GV Grishina IS Veselov IV Trushkov
M V Lomonosov Moscow State University Department of Chemistry
This communication is described the creation of a new nanobiosystems with high antivirus potential
based on the two pharmacophoric fragments - derivatives of fullerene C60 and piperidine ligands
Design of nanoadditive on the basis of two pharmacophoric fragments - functional derivatives of
trans-34-dihydroxypiperidine and organically modified by fullerene C60 can be a very promising
bioactive substances Such a perspective is related to using first as ligands several trans-34-
dihydroxylated piperidines already demonstrated anti-HIV activity and secondly the uniqueness of
fullerene spheroid significantly reduce the toxicity of biologically active adducts We believed that
binding of two biologically active units in the same system will be very useful and promising
N
YX
COOEtON
Me NY
X
1 X = H Y = OH
2 X = Y = OH
3 X =NHR Y = OH
4
Monoadducts 1-4 have obtained by the Benguel and Prato reactions respectively and have since
received 12 new fullerene adducts based on the derivatives of the trans-34-dihydroxypyridine and
trans-4-amino-3-hydroxypiperidines Isolation and identification of these adducts were made using
column and preparative chromatography on silica gel structure and stereochemistry were
established with the involvement required in each case spectral methods including mass
spectrometry and МАLDI X-ray analysis and 1H
13C NMR The main difficulty in undertake
researches consisted of significant differences reactivity due to high lipophilicity derivatives of
fullerene and high hydrophilicity piperidine ligands To reduce this difference we have modified
both fragments introduction to piperidine ligands andor in the molecule organically modified
fullerenes functions andor linkers which facilitated further obtaining of target adducts For some
samples of adducts managed to get soluble in alcohol salts A very important factor has been the
elucidation of the impact of structural and stereochemical factors on possible synergies in the
adduct investigation Target adducts are a new type of nanostructures for medical chemistry with
great pharmacological potential
83
OC22
CHIRASAC STUDY ON CHIRAL SPECTROSCOPY AND PHOTOBIOLOGY
H Nakatsuji T Miyahara
Quantum Chemistry Research Institute (QCRI) 1-36 Goryo-Oohara Nishikyo-ku Kyoto 615-8245
Japan
Weak interactions of molecules with solvents andor environments are of crucial importance in
material science and biology but rather difficult to investigate quantitatively Circular dichroism
(CD) spectra reflect sensitively the conformational structures of chiral molecules their (weak)
interactions with solvents andor proteins etc The SAC-CI method gives their CD spectra very
reliably From this fact the SAC-CI method is a useful tool to investigate the conformational
geometries of chiral molecules their interactions with environments etc by comparing their
experimental and SAC-CI theoretical CD spectra We initiated a systematic molecular technology
called ChiraSac (Chirality + SAC-CI) project (see Figure 1) by using the SAC-CI code and other
highly reliable and useful codes on ldquoGAUSSIANrdquo suit of programs [1] We have already applied
this project successfully to several topics of chiral spectroscopy and photobiology [2-4] We will
present here conformational dependence of α-Hydroxyphenylacetic Acid and similarities and
differences between RNA and DNA etc as some recent applications of ChiraSac to chiral
spectroscopy and photobiology
References
[1] M J Frisch G W Trucks H B Schlegel G
E Scuseria M A Robb J R Cheeseman G
Scalmani V Barone B Mennucci G A
Petersson et al Gaussian 09 Gaussian Inc
Wallingford CT 2009
[2] Circular Dichroism Spectra of Uridine
Derivatives ChiraSac Study Tomoo
Miyahara Hiroshi Nakatsuji and Takehiko
Wada J Phys Chem A 118 2931-2941
(2014)
[3] Conformational Dependence of the Circular
Dichroism Spectrum of α-Hydroxyphenyl-
acetic Acid A ChiraSac Study Tomoo
Miyahara and Hiroshi Nakatsuji J Phys
Chem A 117 14065- 14074 (2013)
[4] Helical Structure and Circular Dichroism
Spectra of DNA A Theoretical Study T
Miyahara H Nakatsuji and H Sugiyama J
Phys Chem A 117 42-55 (2013)
84
OC23
A DFT ANALYSIS ON THE ELECTRONIC PROPERTIES OF
METHYLAMMONIUM LEAD IODIDE PEROVSKITE
K Yamashita1 G Giorgi
1 J Fujisawa
2 H Segawa
2
1 - Department of Chemical System Engineering The University of Tokyo Japan
2 - Research Center for Advanced Science and Technology The University of TokyoJapan
Methylammonium (MA) lead iodide perovskite (CH3NH3PbI3) plays an important role in light
absorption and carrier transport in efficient organicminusinorganic perovskite solar cells [1] In my talk
the first theoretical estimation of effective masses of photocarriers and the role of MA cation in
CH3NH3PbI3 will be discussed
Spin-polarized DFT calculations have been performed with the generalized gradient approximation
From the charge density of the two-fold degenerate states ((a) and (b)) of CBM and those ((c) and
(d)) of VBM one can see that photogenerated electrons around CBM and holes around VBM exist
separately results related to the ambipolar transport nature of the material Effective masses of
photogenerated electrons and holes are estimated to be me =023m0 and mh = 029m0
respectively including spinminusorbit coupling (SOC) effects This result is consistent with the long-
range ambipolar transport property and with the larger diffusion constant for electrons compared
with that for holes in the perovskite which enable efficient photovoltaic conversion [2]
We also have focused our attention on the MA cation and studied the role it plays in the
electronicoptical features of the perovskite paying attention mainly to the iodide compound [3] A
comparison is performed between the electronic properties of MAPbI3 organic-inorganic perovskite
and those of the purely inorganic CsPbI3
References 1 J Bisquert J Phys Chem Lett 4 2597 (2013)
2 G Giorgi J Fujisawa H Segawa K Yamashita J Phys Chem Lett 4 4213 (2013)
3 G Giorgi J Fujisawa H Segawa K Yamashita J Phys Chem 118 12176 (2014)
85
OC24
A HYBRID MCMD REACTION METHOD WITH RARE EVENT-DRIVING
MECHANISM ATOMISTIC REALIZATION OF 2-CHLOROBUTANE
RACEMIZATION PROCESS IN DMS SOLUTION
M Nagaoka
Graduate School of Information Science Nagoya University Furo-cho Chikusa-ku Nagoya 464-
8601 Japan Core Research for Evolutional Science and Technology (CREST) Japan Science and
Technology Agency (JST) Honmachi Kawaguchi 332-0012 Japan ESICB Kyoto University
Kyodai Katsura Nishikyo-ku Kyoto 615-8520 Japan
We demonstrate a new efficient hybrid MCMD reaction method with a rare event-driving
mechanism as a practical lsquoatomisticrsquo molecular simulation of large-scale chemically reactive
systems (Figure 1) Application of the method to (R)-2-chlorobutane molecules in NN-
dimethylformamide (DMF) molecules starting in the optical pure state (100 ee) was found to
successfully provide such an atomistic state with ~0 ee the expected purity of (R)- to (S)-
enantiomers of the racemic mixture in chemical equilibrium [1]
This hybrid MCMD reaction method is promising for studies of various properties in chemically
reactive systems [2] and their stereochemistry as well
Figure 1 Schematic representation of the hybrid MCMD reaction method The curly curves
represent the molecular dynamical (MD) moves in phase space following the equations of motion
while the straight lines with arrows represent the Monte Carlo (MC) moves (or transitions) of the
system (right figure) whose dynamical moves would be extremely rare events In the left figure the
configurational distribution in equilibrium peq
is proportional to the exponential factor exp[-βU]
where U is the global potential function The right figure shows regional distributions eg preq
exp[-βUr] in region r etc The connecting points of the two kinds of moves (open circles) are
selected according to the criteria for chemical reaction occurrence Note that they do not represent
real connections since these points correspond to almost identical states in configuration space but
not in momentum space and with different configurational gradients Wrrarrs and Wsrarrt are the
transition probabilities from state r to s and from s to t respectively [1]
[1] Masataka Nagaoka Yuichi Suzuki Takuya Okamoto Norio Takenaka Chem Phys Lett 583
80 (2013)
[2] N Takenaka Y Suzuki H Sakai M Nagaoka J Phys Chem C 118 10874 (2014)
86
OC25
CALIX[4]ARENE-TETRATHIAFULVALENE RECEPTORS FOR
RECOGNITION OF ELECTRON DEFICIENT GUESTS
VA Azov MH Duker H Schafer D Schluter
University of Bremen
For more than four decades tetrathiafulvalenes1 (TTFs) have been extensively studied on the
account of their outstanding ndashdonating properties Due to their ability to induce reversible
electrochemically-switchable processes1b
TTFs have found their place on the forefront of
supramolecular chemistry Herein we present synthesis and studies of a family of rationally
designed redox-switchable receptors employing monopyrrolo-tetrathiafulvalenes as molecular
recognition units
Our group has been long interested in synthesis and studies of tetrathiafulvalene-containing
molecular architectures and their application for binding of electron-deficient molecular guests2
Recently several upper rim bis-monopyrrolotetrathiafulvalene-calix[4]arene receptors were
synthesized using a modular construction approach3ab
These compounds feature an architecture of
molecular tweezers4 two parallel aligned electron rich TTF arms comprise a molecular recognition
center
Addition of planar electron-deficient guests such as tetracyanoquinodimethane (TCNQ) to a
receptor solution leads to formation of deeply-colored charge-transfer complexes easily visible by a
naked eye Binding titrations were performed to determine the binding constants which reached as
high as 1 104 M
-1 Additionally tripodal receptors comprising three TTF units attached to the
135-substituted-246-triethylbenzene scaffold showed high affinity to pyridinium derivatives in
the gas phase as it was proven by ESI-MS experiments3c
1 a) J L Segura N Martiacuten Angew Chem Int Ed 2001 40 1372ndash1409 b) D Canevet M Salleacute
G Zhang D Zhang D Zhu Chem Commun 2009 2245ndash2269
2 a) V A Azov R Goacutemez J Stelten Tetrahedron 2008 64 1909ndash1917 b) M Skibiński R
Goacutemez E Lork V A Azov Tetrahedron 2009 65 10348ndash10354 c) M H Duumlker R Goacutemez
C M L Vande Velde V A Azov Tetrahedron Lett 2011 52 2881ndash2884
3 a) M H Duumlker H Schaumlfer M Zeller V A Azov J Org Chem 2013 78 4905ndash4912 b) V
A Azov H Schaumlfer D Schluumlter manuscript in preparation c) M-L Lieunang Watat T
Duumllcks D Kemken V A Azov Tetrahedron Lett 2014 55 741ndash744
4 For a review on topologically similar molecular tweezers see F-G Klaumlrner B Kahlert Acc
Chem Res 2003 36 919ndash932
87
OC26
ENHANCED RATE AND SELECTIVITY BY CARBOXYLATE SALT AS A
BASIC COCATALYST IN CHIRAL NHC-CATALYZED ASYMMETRIC
ACYLATION OF SECONDARY ALCOHOLS
K Yamada
Graduate School of Pharmaceutical Sciences Kyoto University Yoshida Sakyo-ku Kyoto 606-
8501 Japan
Kinetic resolution of racemic secondary alcohols via enantioselective acylation is an important
process in synthetic chemistry1 During a study to extend our previous report
2 we found that the
rates and enantioselectivities of chiral NHC-catalyzed asymmetric acylation of alcohols with an
adjacent H-bond donor functionality are remarkably enhanced in the presence of a carboxylate
cocatalyst The degree of the enhancement is correlated with the basicity of the utilized carboxylate
Using a cocatalyst and newly developed electron-deficient chiral NHC kinetic resolution and
desymmetrization of cyclic diols and amino alcohols are achieved with extremely high selectivity
(up to krel = 218 and 99 ee respectively) with low catalyst loading (05 mol )3
References
1 Muumlller C E Schreiner P R Angew Chem Int Ed 2011 50 6012
2 Kuwano S Harada S Oriez R Yamada K Chem Commun 2012 48 145
3 Kuwano S Harada S Kang B Oriez R Yamaoka Y Takasu K Yamada K
J Am Chem Soc 2013 135 11485
88
OC27
CONFORMATIONAL FLEXIBILITY INTRA- AND INTERMOLECULAR
INTERACTIONS AND CATALYTIC ACTIVITY OF PC(sp3)P PINCER
IRIDIUM HYDRIDE COMPLEXES
NV Belkova1 GA Silantyev
1 OA Filippov
1 S Musa
2 D Gelman
2 LM Epstein
1 ES
Shubina1
1 - AN Nesmeyanov Institute of Organoelement Compounds RAS Moscow Russia
2 - The Hebrew University of Jerusalem Jerusalem Israel
A variety of recently developed catalysts operate via different ligand-metal cooperating
mechanisms and new ldquonon-innocentrdquo ligands and their complexes keep appearing in the literature
Reversible switching between different coordination modes found in these compounds opened new
practical reactivity patterns in non-oxidative (ie alternative to the conventional oxidative
additionreductive elimination sequence) activation and formation of polar and non-polar bonds At
that many such systems contain stereochemically rigid pincer ligands and keep their geometry
during the catalytic runs
Bifunctional dibenzobarrelene-based PC(sp
3)P pincer iridium complex 1 is known as an efficient
catalyst in acceptorless dehydrogenation of alcohols [1] and hydrogenationhydroformylation of
alkenes [2] In order to shed light on the mechanism of the hydrogen formationactivation we
performed variable temperature IR and NMR (1H
31P) analysis of intra- and intermolecular
interactions involving hydride ligand and hydroxymethyl cooperating group in 1 and its analogues
The results of the spectroscopic measurements in different media (dichloromethane toluene
DMSO and mixed solvents) were compared with the quantum chemical (DFT M06 and B3PW91
AIM) calculations The data obtained imply flexibility of the dibenzobarrelene-based scaffold
unprecedented for conventional pincer ligands Both the complex 1 and its counterpart 2 prefer
facial configuration of the PCP ligand with P-Ir-P angle of ca 100ordm Such geometries are dictated by
stabilizing IrmiddotmiddotmiddotO interaction and differ by the mutual arrangement of the H and Cl ligands The
complexes show dynamic equilibrium between two most stable fac-isomers which can be
transformed into the meridional ones in the presence of coordinating additives (CH3CN DMSO or
CO but not Et3N) some of which have been used as auxiliary base in catalytic alcohols
dehydrogenation [1] The mechanism of the H2 activation and C-H bond formation involves
intramolecular cooperation between the structurally remote CH2OH functionality and the metal
center and proceeds without the change of the oxidation state of the metal
This work was financially supported by the Russian Foundation for Basic Research (projects No
14-03-00594 and 14-03-31828) and by the German-Russian Interdisciplinary Science Center (G-
RISC) funded by the German Federal Foreign Office via the German Academic Exchange Service
(DAAD) (projects No C-2011b-4 and C-2012a-4) 1 S Musa I Shaposhnikov S Cohen D Gelman Angew Chem Int Ed 2011 50 3533-3537
2 Musa S Filippov O A Belkova N V Shubina E S Silantyev G A Ackermann L Gelman D
Chem Eur J 2013 19 16906-16909
89
OC28
RECENT DEVELOPMENT OF THE FRAGMENT MOLECULOR ORBITAL
METHOD
K Kitaura
Department of Computational Science Graduate School of System Informatics Kobe University
Chuo-ku Kobe 650-0047 Japan
The fragment molecular orbital (FMO) method[1] is an approximate ab initio MO computational
method for vary large molecules such as proteins In the method a molecule is divided into
fragments and ab initio MO calculations are performed on the fragments their dimers and
optionally trimers to obtain the total enegy and other properties of the whole molecule The method
reproduces regular ab initio properties with good accuracy Various FMO-based correlation
methods have been developed including density functional theory (DFT) 2nd
order Moslashller-Plesset
perturbation theory (MP2) coupled cluster theory (CC) and MCSCF Polarisable continuum model
(PCM) was interfaced with FMO allowing one to treat solvent effects of real size proteins The
FMO codes been incorporated in GAMESS-US[2]
Recently We have developed the analytical energy gradients [3] and the second derivatives[4] in
FMO In this presentation I will talk about the applications to geometry optimization MD
simulation and vibrational frequency calculations of large molecular systems
[1] ldquoThe faragment Molecular Orbital Method Practical Applications to Large Molecular Systemsrdquo
DmitriGFedorov Kazuo Kitaura Eds CRC press Boca Raton 2009
[2] GAMESS httpwwwmsgameslabgovgamess
[3] T Nagata et al J Chem Phys 135 044110 (2011)
[4] H Nakata et al J Chem Phys 138 164103 (2013)
90
OC29
MODELING ADSORPTION IN NANOSCALE DEFECTIVE Pd2-GRAPHENE
SYSTEMS
MV Polynski VP Ananikov
ZIOC RAS Leninsky prospekt 47 119991 Moscow Russia MSU Faculty of Chemistry 1-3
Leninskiye Gory 119991 Moscow GSP-1 Russia
Quantum chemical modeling of transition metal particle adsorption on defeted graphene is still
challenging due to the fact that periodic systems of tens or even hundreds of atoms have to be
considered We use DFT methods to evaluate Pd2 affinity to defect sites on graphene surface
GPW method [1] implemented in CP2k program [2] (version 26 development) was used for all the
computations presented Spin-polarized computations with dispersion-corrected PBE-D3 functional
were performed in all cases unless specified explicitly GTH-type pseudopotentials for PBE
functional and DZVP-MOLOPT-SR-GTH basis set were used The model systems were treated as
2D-periodic unless specified explicitly The geometry optimizations were performed with the BFGS
algorithm Cell parameters were kept fixed during geometry optimizations
Pd2 molecules were placed near a defect in several spatial configurations and this model systems
were subjected to geometry optimization The affinity of Pd2 species to various point- and 1D-
defects and steppings was evaluated and both magnetic and non-magnetic states were found The
PBE-D3 method allowed to model a system with both covalent and non-covalent interactions
Noteworthy the model systems are truly nanoscale (the cell vectors are longer than ~2 nm) and
contain up to ~430 atoms
Optimized structures of Pd2 binded to double vacancy defect site (left)
and Stone-Wales-type defect site (right)
The reported study was supported by the Supercomputing Center of Lomonosov Moscow State
University [3]
[1] VandeVondele J Krack M Mohamed F Parrinello M Chassaing T Hutter J Comp
Phys Commun 2005 167 103
[2] Hutter J Iannuzzi M Schiffmann F VandeVondele J Wiley Interdisciplinary Reviews
Computational Molecular Science 2014 4 15
[3] Sadovnichy V Tikhonravov A Voevodin Vl Opanasenko V Lomonosov
Supercomputing at Moscow State University In Contemporary High Performance Computing
From Petascale toward Exascale Vetter J S Ed Chapman amp HallCRC Computational
Science CRC Press Boca Raton USA 2013 pp 283-307
91
OC30
CLUSTER EFFECT IN DECHLORINATION OF ORGANOCHLORIDES BY
BIMETALLIC Au-Ag SYSTEM EXPERIMENTAL AND THEORETICAL
STUDY
LV Romashov LL Khemchyan EG Gordeev VP Ananikov
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky prosp 47
Moscow 119991 Russia
Environmental pollution by various chlorinated organic compounds is the problem of great
importance nowadays Various aliphatic and aromatic chlorides have found applications as solvents
dry cleaning fluids degreasing agents pesticides insecticides etc and have been produced in large
quantities during the last decades Extensive use and chemical stability of chlorinated compounds
led to widespread contamination of environment by these pollutants[1]
In recent decades interesting results were achieved using bimetallic systems as promoters of
dechlorination process Interaction between different metal atoms results in superior properties
which significantly exceed a simple combination of individual metals[2-5]
In spite of very
promising potential the origin of bimetallic effect remains unclear and mechanistic picture of
bimetallic dechlorination is an open question
Experimental study of dechlorinative activity of AuAg bimetallic system has shown formation of a
variety of chlorinated bimetallic AuAg clusters with well-defined AuAg ratio from 11 to 41
(Figure 1) It is the formation of the AuAg cluster species that mediated C-Cl bond breakage since
neither Au nor Ag species alone exhibited a comparable activity (Figure 2) The nature of the
products and the mechanism of dechlorination were investigated by ESI-MS GC-MS NMR and by
quantum chemical calculations at the M066-311G(d)ampSDD level of theory It was revealed that
formation of bimetallic clusters facilitated dechlorination activity due to thermodynamic factor
An appropriate AuAg ratio for efficient hydrodechlorination process was determined in a joint
experimental and theoretical study carried out in the present work High activity of the designed
bimetallic system made it possible to carry out dechlorination process under mild conditions at
room temperature
Figure 1 Example of detected bimetallic
cluster (optimized geometry)
Figure 2 Bimetallic effect in dechlorination
reaction
[1] Thornton J Pandoras Poison Chlorine Health and a New Environmental Strategy MIT
Press MA 2000
[2] Nutt M O Hughes J B Wong M S Environ Sci Technol 2005 39 1346-1353
[3] De Corte S Sabbe T Hennebel T Vanhaecke L De Gusseme B Verstraete W Boon
N Water Res 2012 46 2718-2726
[4] De Corte S Hennebel T Fitts J P Sabbe T Biznuk V Verschuere S van der Lelie D
Verstraete W Boon N Environ Sci Technol 2011 45 8506-8513
[5] Lambert S Ferauche F Brasseur A Pirard J P Heinrichs B Catal Today 2005 100 283-
289
92
OC31
PORPHYRIN-FULLERENE DYADS COVALENTLY LINKED VIA
PYRROLO[34-C]PYRROLE LINKER ON THE WAY TO MOLECULES
FORMING LONG-LIVED CHARGE-SEPARATED STATE
AS Konev PI Prolubnikov AF Khlebnikov AS Mereshchenko AV Povolotskiy OV Levin
St Petersburg State University Institute of Chemistry St Petersburg Russian Federation
Porphyrinofullerenes represent promising materials for artificial photosynthesis and for construction
of organic photovoltaic devices1 due to their ability to form charge-separated state (CS) upon
irradiation with light The lifetime of the CS thus formed ranges from pico-2
to microsecond3 range
depending on the structure of the dyad and on the conditions of irradiation The larger the lifetime
of the CS the higher is the probability of worthwhile intermolecular electron transfer from a
photochemically generated radical-ion pair making thus a creation of the systems that are capable
to form a long-lived CS an important task
Analysis of the relevant literature shows that a porphyrin-fullerene dyad with rigid linker that
enables spatial separation of the chromophors and fixes them in face-to-edge orientation so that
their π-systems are virtually orthogonal one to another should reduce the rate of back-electron
transfer and enhance thus the lifetime of the CS Keeping in mind this strategy of achieving long-
lived CS species we synthesized a series of covalently linked porphyrin-fullerene dyads with a
rigid pyrrolo[34-c]pyrrolic linker that meets the above requirements and studied them by means of
transient absorption spectroscopy and cyclic voltammetry The lifetime of the charge separated state
constituted up to 4 μs depending on the substituents in the porphyrin core The effect of the
porphyrin substituent on the lifetime of the CS was rationalized on the basis of DFT and TD-DFT
B3LYP(6-31G(d)) calculations of ground and excited electronic states of model compounds
N
CO2Et
CO2Et
N N
EtO2C
EtO2C
O
ON
NH N
HN
Ar
Ar
Ar
Ar-CHO
HN
N
O
O
O
CO2EtO
CO2Et
NN
H2N
NH2
532 nm
F Pup to 4 μs
References
1 D M Guldi Chem Soc Rev 2002 31 22
2 eg NV Tkachenko H Lemmetyinen J Sonoda K Ohkubo T Sato H Imahori Sh
Fukuzumi J Phys Chem A 2003 107 8834
3 eg ME El-Khouly K-J Han K-Y Kay Sh Fukuzumi Eur J Chem Phys Phys Chem
2010 11 1726
The work was financially supported by the Russian Foundation for Basic Research (Grant No 14-
03-00187) St Petersburg State University (Grants No 1238782012 125015622013) and St
Petersburg State UniversityDAAD joint program (A117833512235082012)
93
OC32
PALLADIUM-CATALYZED CASCADE ANNULATION OF ALKYNES
WITH UNACTIVATED ALKENES IN IONIC LIQUIDS
J-X Li S-R Yang H-F Jiang
South China University of Technology School of Chemistry and Chemical Engineering
Guangzhou P R China
Transition metal-catalyzed carbon-carbon orand carbon-heteroatom bond formations have attracted
considerable attention over the past decades owing to their easy access to highly functionalized
molecules in an efficient atom- and step-economical way[1]
Particularly palladium-catalyzed
cascade reactions have been emerging as a captivating branch of organic chemistry associating
with the mild reaction conditions and excellent functional group tolerance in a fashion of green
chemistry[2]
On the other hand ionic liquids offer an alternative and ecologically sound medium in
comparison to conventional organic solvents as they are nonvolatile recyclable highly compatible
with transition metal catalysts limited miscibility with common solvents enables easy product and
catalyst separation with the retention of catalyst activity in the ionic phase[3]
Recently we have investigated various palladium(II)-catalyzed cascade transformations of alkynes
and alkenes in ionic liquids (Scheme 1 Path I-III) As part of our research programs in
nucleopalladation and Pd-catalyzed cross-coupling reactions in ionic liquids we herein present the
first example of palladium-catalyzed intermolecular cascade annulation of alkynes with unactivated
alkenes in ionic liquids to afford a series of functionalized alkene products (Scheme 1 Path IV)
Scheme 1
Reference
[1] Gulevich A V Dudnik A S Chernyak N GevorgyanV Chem Rev 2013 113 3084
[2] Wu W Jiang H Acc Chem Res 2012 45 1736
[3] Giernoth R Angew Chem Int Ed 2010 49 2834
94
OC33
SYNTHESIS OF BENZOTHIADIAZOLE COMPOUNDS FOR OPTICAL
MATERIALS
YL Li SH Chen
Institute of Chemistry Chinese Academy of SciencesCAS Key Laboratory of Organic Solids
Beijing PR China
The nature of the substituent groups greatly influences the structural and photophysical properties
of DA molecules The nature of the linkage between the D and A units also influences the
structures and photophysical properties of intramolecular charge transfer (ICT) compounds1 For
example in the DA molecules BSC and BEC containing carbazole moieties as their D moieties
and a NO2-substituted benzothiadiazole as their A moiety X-ray crystal data elucidated multiple
intermolecular interactions in these systems2 These interactions were the main driving forces
directing the self-organization of the microstructures with the different linkages exhibiting
distinctly different self-assembly behavior Most DA-substituted compounds suffer from
aggregation-caused emission quenching (ACQ) in the solid phase greatly limiting their
applications3 We have observed aggregation-induced emission (AIE) effects for several of our ICT
compounds including the carbazole- and benzothiadiazole-based BSE BEC BTN-6 and BTN-7
These prepared nanostructures exhibit green yellow and especially red emissions In addition the
distance-dependent photoluminescence image of a single microrod of BTN-7 measured using a
near-field scanning optical microscope indicated that these microrods possess outstanding optical
waveguide properties with a waveguide efficiency (a) of 0018 dB μmndash1
and no obvious red-shift4
References
1 Liu H Xu J Li Y Li Y Acc Chem Res 2010 43(12) 1496ndash1508
2 Chen S Qin Z Liu T Wu X Li Y Liu H Song Y Li Y Phys Chem Chem Phys
2013 15 12660ndash12666
3 Xu J Zheng H Liu H Zhou C Zhao Y Li Y Li Y J Phys Chem C 2010 114 2925ndash
2931
4 Chen S Chen N Yan Y Liu T Yu Y Li Y Liu H Zhao Y Li Y Chem Commun
2012 48 9011ndash9013
95
OC34
DENDRIMERS AND BIOMASS SYNTHESIS CATALYSIS AND
ENCAPSULATION
S Bouquillon B Menot J Stopinski
ICMR Universitй Reims Champagne Ardenne
For several years our research team is interested in the development of new families of dendrimers
using organic by-products from biomass (pentoses glycerin or corresponding by-products) Some
glyco-or glycerodendrimers derived from PPI (polypropylene imines) were already obtained and
valued in the domains of aqueous catalysis and encapsulation of metallic salts or emergent
pollutants [12]
Glycodendrimers were also previously synthetized and used for the preparation and the stabilization
of metallic nanoparticles (Pt Pd Au) which could be used in aqueous catalysis [3]
The objective of this presentation is at first to describe the synthesis of nitrogenous
glycerodendrimers derived of polypropyleneimines (PPis) or of polyAmidoAmines (PAMAMs)
and secondly to demonstrate their potential in catalyses of hydrogenation and oxidation in the
water and in encapsulation of organic pollutants (Figure 1)
Figure 1 Catalysis and encapsulation in biomass derived dendrimers
[1] C Hadad J-P Majoral J Muzart A-M Caminade S Bouquillon Tetrahedron Lett 2009 50
1902
[2] S Balieu A El Zein R De Sousa F Jeacuterocircme A Tatiboueumlt S Gatard Y Pouilloux J Barrault
P Rollin S Bouquillon Adv Synth amp Catal 2010 352 1826
[3] a) S Gatard L Liang L Salmon J Ruiz D Astruc S Bouquillon Tetrahedron Lett 2011 52
1842 b) S Gatard L Salmon C Deraedt J Ruiz D Astruc S Bouquillon Eur J Inorg
Chem 2014 2671
96
OC35
BIOINSPIRED CHIRAL IONIC LIQUIDS AS INNOVATIVE
ORGANOCATALYSTS
LC Branco
REQUIMTE Departamento de Quнmica Faculdade de Ciкncias e Tecnologia Universidade Nova
de Lisboa 2829-516 Caparica Portugal
Chiral Ionic Liquids (CILs) can be useful as chiral solvents or chiral selector in some cases [1]
Recent examples showed the possibility to use chiral ILs as efficient organocatalysts or chiral
ligands for Asymmetric Aldol and Michael additions as well as Sharpless dihydroxylation of
olefins among others [23] Asymmetric organocatalysis is an intensively developing area of
current organic chemistry in recent years [4] Aldol and Michael reactions play an important role in
carbon-carbon bond forming reaction The interest of chiral molecules as novel catalysts remains to
grow as a wide range of small organic molecules including L-aminoacids moieties such as L-
proline and L-cysteine which showed to be efficient organocatalysis for asymmetric reactions [5]
In this context we have been developed novel Bioinspired chiral ionic liquids based on L-cysteine
and L-proline derivatives as well as task-specific nucleotides in order to test as chiral organocatalyst
of asymmetric organocatalysis and metal catalysis direct aldol reactions between ketones with
nitrobenzaldehydes For some cases it was possible to obtain the pure chiral products in good
yields and enantiomeric excesses comparable with the conventional systems Asymmetric direct
aldol reactions Michael additions Suzuki and Mannich reactions using some bioinspired CILs as
chiral catalyst were also tested Catalytic recycling processes have been performed using efficient
sustainable methodologies
Acknowledgements This work has been supported by FCTMCTES (PEst-CEQBLA00062011
PTDCCTM1036642008 and PTDCCTM-NAN1206582010 projects)
References [1] J Ding D W Armstrong Chirality 2005 17 281
[2] a ) A Lu T Liu R Wu Y Wang G Wu Z Zhou J Fang C Tang J Org Chem 2011 76
3872 b) L C Branco P M P Gois N M T Lourenco V B Kurteva C A M Afonso Chem
Comm 2006 2371
[3] a) L C Branco A Serbanovic M N Ponte C A M Afonso ACS Catal 2011 1 1408 b)
C A M Afonso L C Branco N R Candeias PMP Gois N M T Lourenccedilo N M M
Mateus J N Rosa Chem Commun 2007 2669
[4] K Bica P Gaertner Eur J Org Chem 2008 3235
[5] B List R A Lerner C F Barbas III J Am Chem Soc 2000 122 2395
BioinspiredChiral Ionic Liquid
Asymmetric
catalysis
Chiral
Recognition
BioinspiredChiral Ionic Liquid
Asymmetric
catalysis
Chiral
Recognition
97
OC36
THE COMPARISON OF COMPUTATIONAL METHODS FOR THE STUDY
OF PYRANOSIDE-INTO-FURANOSIDE REARRANGEMENT
AG Gerbst VB Krylov DA Argunov NE Nifantiev
ND Zelinsky Institute of Organic Chemistry RAS Laboratory of Glycoconjugate Chemistry
Moscow Russia
Furanoside units are often encountered in biologically important complex polysaccharides and
smaller oligosaccharides On the other hand synthetic methods of furanoside modification are less
developed than those for pyranosides Thus a promising strategy for the introduction of a furanoside
moiety into a complex saccharide might be to synthesize first the corresponding pyranoside and
then convert it into the pyranoside Recently in our laboratory we have discovered a novel
rearrangement that allows such transformation of a pyranoside into furanoside (PIF) with good
yields This reaction proceeds under per-sulfation conditions in the acid media
In this communication we present the comparison of different quantum chemical methods for the
computational study of the PIF mechanism (Fig 1) It includes the energy calculations of starting
molecules and supposed transition states (TS) and intermediates Obtained data are correlated with
the observed reaction kinetics
-
HO3SO
-
--
-
-
HOH2C
HOH2C
OSO3
O3S
-
-TS1TS2
post-reaction complex
Figure 1 Proposed mechanism of the PIF transformation
Ab initio calculations were used in this work with different split-valence basis sets Taking 6-31G
type basis sets we varied number of diffuse and polarization functions in order to find the optimal
basis set which would allow fast calculation with reasonable accuracy Finally basis set 6-31+G
having one diffuse and one polarization function was found to give most satisfactory results
Acknowledgement This work was supported by the grant from Division of Chemistry and
Material Sciences of Russian Academy of Sciences Program 1
98
OC37
GOLD(I) CATALYSED ASYMMETRIC HYDROAMINATION OF
ALKENES IN MILD CONDITIONS
F Agbossou-Niedercorn1 MA Abadie
1 F Medina
1 X Trivelli
2 F Capet
1 C Michon
1
1 - University Lille Nord de France UCCS UMR 8181 CNRS ENSCL C7 CS90108 59652
Villeneuve d Ascq Cedex France
2 - University Lille Nord de France LGSF UMR 8576 USTL 59655 Villeneuve d Ascq Cedex
France
Gold catalysed hydroamination reactions were recently highlighted on alkenes1ab
allenes1c
and
dienes1ad
substrates for both intra- and intermolecular reactions However achieving highly
selective gold catalysed hydroamination of alkenes activated or not remains a challenging
endeavor and we would like to report herein our last results2
First following our researches on activated alkenes2ab
and allenes2c
the intramolecular gold(I)
catalysed asymmetric hydroamination of alkenes was studied screening a wide range of
monophosphines Specially designed phosphoramidite ligands proved to lead to active mononuclear
gold(I) catalysts when combined with silver salts Indeed chiral amines were obtained in high
yields and average enantioselectivities using mild reaction conditions (Scheme 1)2d
Second various binuclear gold(I) catalysts based on selected diphosphine ligands were studied
When combined with a silver salt a specific gold(I) species proved to perform efficiently the
intramolecular hydroamination of alkenes at mild temperatures with high yields and
enantioselectivities (Scheme 1)2e
The molecular structure of catalyst was determined by X-Ray
diffraction analyses and DOSY NMR experiments in order to check the influence of silver salts and
water3 Indeed water proved to enhance significantly reaction yields and enantioselectivities
Scheme 1
1 (a) X Giner C Naacutejera GKovaacutecs A Lledoacutes G Ujaque Adv Synth Catal 2011 353 3451 (b) M
Kojima K Mikami Synlett 2012 23 57 (c) K L Butler M Tragni R A Widenhoefer Angew Chem
Int Ed 2012 51 5175 (d) O Kanno W Kuriyama J Z Wang D F Toste Angew Chem Int Ed
2011 50 9919
2 (a) F Medina C Michon F Agbossou-Niedercorn Eur J Org Chem 2012 6218 (b) F Medina et al
Comptes Rendus Chimie 2013 16 311 (c) C Michon F Medina M-A Abadie F Agbossou-
Niedercorn Organometallics 2013 32 5589 (d) C Michon M-A Abadie F Medina F Agbossou-
Niedercorn Catalysis Today 2014 doi 101016jcattod201401030 (e) M-A Abadie X Trivelli F
Medina F Capet F Agbossou-Niedercorn C Michon submitted
3 (a) A Homs I Escofet A M Echavarren Org Lett 2013 15 5782 (b) Y Tang B Yu RSC Adv
2012 2 12686 (c) D Wang R Cai S Sharma J Jirak S K Thummanapelli N G Akhmedov H
Zhang X Liu J L Petersen X Shi J Am Chem Soc 2012 134 9012
99
OC38
SUPRAMOLECULAR GELS FOR CATALYTIC TRANSFORMATIONS
AND NANO-MATERIALS SYNTHESIS
S Vatsadze V Nuriev A Medvedrsquoko
Chemistry Department Lomonosov Moscow State University
Supramolecular gels are gels formed by immobilizations of liquid phase on the 3D network of
entangled nano-fibres which themselves are the result of supramolecular polymerization and self-
organization [1] In this report we will focus on the following
1 supramolecular gels belongs to the family of laquosmart materialsraquo since they could change their
structures in response to the external stimuli
2 the control over structural and practical properties of gels could be engineered at the stage of
molecule design
3 the possibility of using the organogel as a template for the synthesis of the inorganic replica
4 post-synthetic transformations ie supercritical fluid drying expands the scope of materials
properties
5 metal-containing supramolecular gels combine the properties of both heterogeneous and
homogeneous catalysts
We thank financial support by RFBR (grant 14-03-91160)
1 VPAnanikov LLKhemchyan YuVIvanova VIBukhtiyarov AMSorokin IPProsvirin
SZVatsadze AVMedvedko VNNuriev ADDilman VVLevin IVKoptyug
KVKovtunov VVZhivonitko VALikholobov AVRomanenko PASimonov
VGNenajdenko OIShmatova VMMuzalevskiy MSNechaev AFAsachenko
OSMorozov PBDzhevakov SNOsipov DVVorobyeva MATopchiy MAZotova
SAPonomarenko OVBorshchev YNLuponosov AARempel AAValeeva
AYuStakheev OVTurova ISMashkovsky SVSysolyatin VVMalykhin
GABukhtiyarova AOTerentev IBKrylov Development of new methods in modern
selective organic synthesis preparation of functionalized molecules with atomic precision
RussChemRev 2014 83 (10) in press DOI 101070RC2014v083n10ABEH004471
100
OC39
SYNTHESIS AND TRANSFORMATIONS OF STRAINED POLYNITROGEN
COMPOUNDS
MA Kuznetsov AS Pankova
Saint Petersburg State University Institute of Chemistry Saint Petersburg Russia
The oxidation of many N-aminoheterocycles in the presence of unsaturated compounds is a general
way to N-aminoaziridine derivatives containing a strained three-membered ring and combining two
heterocyclic moieties in one molecule via a weak N-N bond This reaction the so-called oxidative
aminoaziridination is applicable to a wide range of unsaturated substrates and proceeds in a
stereospecific manner with a complete retention of a spatial arrangement of substituents at gtC=Clt
bond in the resulted N-aminoaziridines In this way we have synthesized a set of alkynylaziridines
which possess three endothermic fragments in one molecule and large series of adducts to styrenes
unsaturated carbonyl compounds a lot of spiroaziridines etc
With alkenylpyrazoles the expected heterocyclic chains are usually formed in good yields And it
was the same for alkenyl-124- and 134-oxadiazoles with one or two double bonds in the side
chains The reaction with alkenylfuranes leads to the unsaturated acyclic compounds exclusively
and can be used for a stereospecific synthesis of 4-oxohexa-25-dienal derivatives with
(Z)-configuration of 23-C=C bond The oxidative aminoaziridination of the very similar alkenyl-
thiophenes leads to expected adducts onto exocyclic C=C bond but with thiophene itself and even
with selenophene gave the very interesting tricyclic diadducts though in low yields
Since the classical works of R Huisgen in 60-ies it is well known that the C-C bond in aziridines
can be broken thermally or upon irradiation giving the octet-stabilized 13-dipoles so-called
azomethyne ylides which can be involved in 13-dipolar cycloaddition reactions We have found
that for cis- and trans-23-disubstituted 1-phthalimidoaziridines this set of transformations proceeds
in a stereospecific manner as a concerted process which obeys the rules of orbital symmetry
conservation The intramolecular cycloaddition of 13-dipoles should lead to the polycyclic
condensed compounds which are of interest in many aspects And we have realized it for some N-
phthalimidoaziridines with sterically accessible but inactivated C=C and CequivC bonds
In some cases the regioisomeric imines appeared as the main components of these reaction
mixtures This result caused by 12-migration of phthalimidyl rest in the intermediate ylides is often
the general one for arylsubstituted aziridines On another hand an attempt for intramolecular
cycloaddition of aziridines with carbonyl substituents led to quite another products the 15-
electrocyclization of an intermediate ylide with a participation of C=O bond followed by loss of
phthalimide fragment provided aromatic oxazoles in good yields This transformation of carbonyl-
substituted azomethyne ylides into oxazoles competes with an intermolecular cycloaddition too
The yields of oxazoles in all these reactions usually vary from good up to excellent Taking it into
account we have offered the simple and efficient transformation of αβ-unsaturated carbonyl
compounds into the corresponding oxazoles via N-phthalimidoaziridines or even via N-aryl-
sulfonylaziridines This approach is applicable to the synthesis of oxazoles with ethynyl substituent
as well In the case of C-alkenylaziridines the intermediate ylide contains a conjugated C=C bond
and another kind of 15-electrocyclization ndash into pyrrolines ndash is conceivable
Combination of the strained three-membered rings and hydrazine moiety makes cyclopropyl-
hydrazines highly energetic compounds Beside it the hydrazine fragment occurs in a variety of
bioactive compounds But only two ndash mono- and 12-dicyclopropylhydrazine ndash out of five possible
cyclopropylhydrazines have been known till now And the last part of our work is devoted to the
synthesis of still unknown cyclopropylsubstituted hydrazines This work was supported by Russian Scientific Fond (research grant no 14-13-00126)
101
OC40
NEW TYPE OF REACTIVITY OF DONOR-ACCEPTOR
CYCLOPROPANES GaCl3-MEDIATED GENERATION OF FORMAL 12-
AND 14-DIPOLES
RA Novikov AV Tarasova YV Tomilov
N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences 47 Leninsky prosp
119991 Moscow Russian Federation
A new type of reactivity of donor-acceptor cyclopropanes has been discovered On treatment with
anhydrous GaCl3 they react as sources of even-numbered 12- and 14-dipoles instead of the
classical odd-numbered 13-dipoles due to migration of positive charge from the benzyl center This
type of reactivity has been demonstrated for new reactions viz cyclodimerizations of donor-
acceptor cyclopropanes that occur as [2+2]- [3+2]- [4+2]- [5+2]- [4+3]- and [5+4]-annulation
The [4+2]-annulation of 2-arylcyclopropane-11-dicarboxylates to give polysubstituted 2-
aryltetralins has been developed in a preparative version that provides exceedingly high regio- and
diastereoselectivity and high yields The strategy for selective cross-combination of donor-acceptor
cyclopropanes was also been developed The mechanisms of the discovered reactions involving the
formation of a comparatively stable 12-ylide intermediate have been studied Hitherto unknown
complexes of donor-acceptor cyclopropanes with GaCl3 belonging to a new type and having a 12-
dipole (ylide) structure have been obtained and characterized by 1D 2D and DOSY NMR
spectroscopy Futher transformations of this complex have also been demonstrated
C O2M e
C O2M e
A r
A r C O2M e
C O 2M e
C O 2M eM e O
2C
A r
M e O 2C
M e O2C
R
R 3
R 4
R 5
R 2
R 1
C O2M e
C O 2M e
A r
A r
M e O 2C
M e O 2C
C O 2M e
C O 2M e
N e w 1 2 - a n d 1 4 -D ip o la r
S y n th e t ic E q u iv a le n ts
[4 + 2 ] [2 + 2 ]
G a C l3
C la s s ic a l 1 3 -D ip o le
The discovered [4+2]-annulation of DAC is a synthetically valuable process that allows the one-
stage assembly of polysubstituted tetralins with exceptionally high regio- and diastereoselectivity
The latter may be of interest as synthons in organic synthesis and as compounds possessing
biological activity In fact the aryltetralin moiety occurs in the structures of a number of
compounds that have been isolated from various natural sources and manifest a broad spectrum of
biological activity including antitumor activity
This work was supported by the Russian Federation President Council for Grants (Program for
State Support of Leading Scientific Schools of the Russian Federation grant no NSh-60420123)
Selected Publications Tetrahedron Lett 2011 52 4996ndash4999 Organometallics 2012 31 8627ndash8638
J Org Chem 2012 77 5993ndash6006 Org Lett 2013 15 350ndash353
Helv Chim Acta 2013 96 2068ndash2080 Angew Chem Int Ed 2014 53 3187ndash3191
102
OC41
NEW REACTIONS OF TANTALUM(V) AMIDES
MN Sokolov AL Gushchin AV Rogachev PA Abramov
Nikolaev Institute of Inorganic Chemistry
Transition metal amides are highly reactive compounds which are much employed as reagents
ligand transfer agents or precursors for more complex molecules The ready cleavage of the highly
polar M-NR2 bond makes the amides particularly important synthons for a wide range of new
compounds and materials The M-NR2 bond can be easily cleaved by protonation using various
reagents with acidic E-H bonds (alcohols thiols secondary phosphines pyrazoles etc) Reactive
small molecules such as CS2 or CO2 undergo insertion with the formation of dithiocarbamates and
carbamates In this work we report synthesis of new Ta coordination compounds and clusters by
reactions of Ta(NMe2)5 with CS2 Ph2PH and pyrazol with or without subsequent treatment with
sulfur Ta(NMe2)5 easily react with CS2 with the formation of [Ta(S2CNMe2)3( -CH2-NMe)] (1)
The formation of 1 can be explained as triple insertion of CS2 followed by α-elimination of a
HNMe2 molecule Excess of CS2 leads to the formation (in CH2Cl2) of [Ta(S2CNMe2)4]Cl (2)
Cyclic voltammetry shows that [Ta(S2CNMe2)4]+ can be reversibly reduced to the neutral
[Ta(S2CNMe2)4] the Ta(V)Ta(IV) couple having E12 ndash 074 V vs AgAgCl Reaction with CS2 in
the presence of S8 leads to a complex mixture of Ta(V) dithiocarbamates [TaS(S2CNMe2)3] (3)
[Ta(S2)(S2CNMe2)3] (4) and a perthiocarbamate complex [TaS(S3CNMe2)(S2CNMe2)2] (5)
HPPh2 rapidly reacts with Ta(NMe2)5 with the formation of an unstable product which after
treatment with S8 yields green crystals of a cuboidal cluster [Ta4S4(μ-S2PPh2)4(S2PPh2)2] (6) which
is to the best of our knowledge the first cluster with the Ta4S4 core Long Ta-Ta distances (297-
305 Aring) correspond to electron-deficient (only six of the required 12 e) M-M bonding in the cluster
core
35-dimethylpyrazol (PzH) is a stronger N-H acid than Me2NH and reacts with Ta(NMe2)5 with the
formation of yellow crystals of the pentakis(pyrazolate) [Ta(pz)5] (7) According to X-ray data the
Ta atom achieves CN 8 by coordinating three pz ligands in the 2 and two pz ligands in the
1
mode All the compounds have been characterized by single crystal X-ray analysis Reactivity of
complexes 1-7 is being investigated
The work was supported by RFBR grant No 12-03-33028
[1] MF Lappert A Protchenko P Power A Seeber Metal-Amide chemistry 2009 John Wiley
and Sons 355 pp
103
OC42
STRUCTURE-REACTIVITY RELATIONSHIPS IN THE REACTIONS OF C-
AMINO-1H-124-TRIAZOLES WITH ELECTROPHILES
VM Chernyshev DA Pyatakov AV Astakhov AI Evdokimova AYu Chernenko
Platov South-Russian State Polytechnic University (NPI) Novocherkassk Russia
Molecules of C-amino-124-triazoles (AT) contain several alternative nucleophilic centers namely
NH2 group and any of the ring nitrogen atoms and therefore can be considered as multifunctional
nucleophilic reagents Such multifunctionality on the one hand opens up exciting possibilities for
the synthesis of various substituted triazoles and condensed heterocycles [1] however on the other
hand it causes the problem of selectivity [2 3] The present report discusses relationships between
the structure of AT and their reactivity towards electrophiles and some novel approaches to the
control of selectivity
On the basis of computational and experimental methods it was established that the position of the
endocyclic substituent R has a significant influence on the reactivity of C-amino-1-R-124-
triazoles The global nucleophilicity of the 1-substituted 3-amino-124-triazoles is higher than the
1-substituted 5-amino-124-triazoles Therewith amino group in the position 3 of triazole ring is
substantially more nucleophilic than in the position 5 The atoms N-2 and N-4 of triazole ring as
well as the 3-NH2 group are the most favorable sites in the 1-substituted C-amino-124-triazoles for
the attack of electrophiles
Some new approaches to the selective synthesis of substituted triazoles and condensed heterocycles
via reactions of AT with electrophilic and bielectrophilic reagents are considered The structural
features and reactions of condensed derivatives of 124-triazole including some new recyclizations
are discussed
Acknowledgements This work was financially supported by the Russian Foundation for Basic
Research (grant no 13-03-00253) and in part by the Ministry of Education and Science of the
Russian Federation State contract No 2014143 (project No 2945) References
[1] Curtis ADM Jennings N 124-Triazoles In Comprehensive Heterocyclic Chemistry III Elsevier
Oxford 2008 V 5 P 159-209
[2] Chernyshev VM Astakhov AV Starikova ZA Tetrahedron 2010 66 3301
[3] Chernyshev VM Pyatakov DA Sokolov AN Astakhov AV Gladkov ES Shishkina SV
Shishkin OV Tetrahedron 2014 70 684
104
OC43
SILYL NITRONATES IN THE NOVEL [3+3]-CYCLOADDITION
REACTION WITH DONOR-ACCEPTOR CYCLOPROPANES
AA Mikhaylov1 RA Novikov
1 DE Arkhipov
2 SL Ioffe
1
1 - N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russian
Federation
2 - AN Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences
Moscow Russian Federation
Cycloaddition reactions are one of the most effective tools for rapid generation of molecular
complexity1 Recently the formal cycloadditions have evoked special attention due to the intriguing
ability of donor-acceptor cyclopropanes mainly 11-cyclopropane diesters 1 to behave as
equivalents of 13-zwitterions under Lewis acid catalysis23
The formal [3+3]-cycloaddition
discovered by Kerr and co-workers on the nitrones in 20034
has already proved itself as a powerful
method for six-membered cycles construction3
In this respect silyl nitronates 2 can be considered as perspective substrates for formal
cycloaddition chemistry due to their 13-dipolaric nature We have shown that different silyl
nitronates 2 derived from both primary and secondary nitro compounds can react with 11-
cyclopropane diesters 1 giving rise to polysubstituted six-membered nitroso acetals 35 The latters
in hand can be easily transformed into isomeric pyrroline-N-oxides 4 and 5 via novel acid-catalyzed
ring contractionsilanol elimination reaction
In the presentation the major regularities of the observed [3+3]-cycloaddition reaction will be
discussed The special attention will be focused on the reasons determining stereochemical outcome
of nitroso acetals 3
The work was supported by Russian Foundation for Basic Research (Grants 12-03-00278 14-03-
31560)
References
1 M Juhl D Tanner Chem Soc Rev 2009 38 2983-2992
2 C A Carson M A Kerr Chem Soc Rev 2009 38 3051-3060
3 T F Schneider J Kaschel D B Werz Angew Chem Int Ed 2014 53 5504ndash5523
4 I S Young M A Kerr Angew Chem Int Ed 2003 42 3023-3026
5 A A Mikhaylov R A Novikov Yu A Khomutova D E Arkhipov A A Korlyukov A A
Tabolin Yu V Tomilov S L Ioffe Synlett submitted
105
OC44
SOLID-PHASE SYNTHESIS OF PINCER COMPLEXES EMERGING
ALTERNATIVE TO CONVENTIONAL SYNTHESIS IN SOLUTION
DV Aleksanyan VA Kozlov
A N Nesmeyanov Institute of Organoelement Compounds Russian Academy of Sciences
Pincer complexes featuring a tridentate monoanionic framework have become a privileged class of
organometallic compounds finding extensive application in catalysis materials science
biochemistry and so on12
Several synthetic routes including direct cyclometalation oxidative
addition and trans(cyclo)metalation give access to pincer complexes with almost any type of
ligands and metal ions however the simplest route seems to be direct cyclometalation Numerous
examples of direct cyclometalation of pincer ligands have been described in solution but the
literature data on the solid-state synthesis of metallacycles are restricted only to several reports
dealing with the thermally induced intramolecular cyclometalation of well-defined coordination
complexes leading to monometallacyclic species Recently we have shown that cyclometalation of
pincer ligands can be readily carried out in the solid state simply by heating homogeneous mixtures
of a ligand and metal precursor obtained by manual grinding in a mortar3 This novel solid-phase
approach has now been extended to a range of pincer-type ligands which require the activation of
the CndashH NndashH and OndashH bonds and have different ancillary S- P- and N-donor groups (for
selected examples see figure) The results obtained show great potential of the solid-phase
cyclometalation as an alternative to the conventional synthesis of complex organometallic
compounds in solution Some aspects of the solid-phase cyclometalation will be discussed based on
the results of spectral and thermochemical analyses
P N
SS
Ph
Pd
Cl
Ph
HN
Ph2PS
N
S
Pd
Cl
P
PhPh
S
N
OP
S
Ph
Ph
PdCl
P
PhPh
S
N
O
SPd
Cl
Me
P
Ph Ph
S
N OPd
Cl
This work was supported by the Russian Foundation for Basic Research (project no 14-03-31237-
mol-a) and the Grant of the President of the Russian Federation for young scientists (project no
MK-38220143)
1 The Chemistry of Pincer Compounds D Morales-Morales and C M Jensen (Eds) Elsevier
New York 2007
2 Organometallic Pincer Chemistry G van Koten and D Milstein (Eds) Topics Organomet
Chem 2013 40
3 V A Kozlov D V Aleksanyan M V Korobov N A Avramenko R R Aysin O A
Maloshitskaya A S Korlyukov and I L Odinets Dalton Trans 2011 40 8768
106
OC45
SYNTHETIC APPROACHES AND ELECTRONIC PROPERTIES OF
FUNCTIONALIZED FULLERENES AS NANOSIZED OPTICAL
MOLECULAR SWITCHES
LM Khalilov AR Tuktarov AR Akhmetov AA Khuzin ZR Shakirova AR Tulyabaev II
Kiryanov VM Yanybin UM Dzhemilev
Institute of Petrochemistry and Catalysis of RAS
At present the abilities of the manufacturing technology of traditional materials for modern
computers have almost peaked The main factor that restrains creation of modern supercomputers is
a critical size of silicon transistors to be reached which are responsible for a quick response One
possible way to solve the problem is to replace conventional silicon transistors by molecular
switches that can be by several orders less than the known smallest devices
Given that the molecular switches must have π-donor groups along with π-acceptor one we have
put forward the idea to use fullerene derivatives a new allotropic carbon form that possess high
donor-acceptor features Thus a new effective methods of synthesis of potential molecular switches
and three-dimensional memory elements based on C60 and C70 fullerene derivatives have been
suggested Highly selective methods of cycloaddition of organic azides to fullerenes under metal-
complex catalysts have been developed This gives the individual aziridine- and azahomofullerenes
that able to isomerize into each other under influence of UV irradiation
Algorithms of dichotomous features which are responsible for photochromic properties of
molecular switches and generating of the new structures with incorporated fullerenes as doping
agents directly into the fullerene core and in the attached moieties to activate the donor-acceptor
properties and stability of molecular electronic systems The results of molecular design of new
types of optical molecular switches will be done using calculations of the electronic structure and
physicochemical properties of fullerene derivatives with modern high-level quantum chemistry
approaches (DFT and ab initio) will be discussed
107
OC46
COORDINATION CHEMISTRY OF BIS(PYRAZOLYL)PYRIDINES WITH
3d-TRANSITION METALS RECENT DEVELOPMENT AND PROGRESS
NM Kurnosov
Lomonosov Moscow State University Department of Chemistry Moscow Russia
Coordination compounds of transition elements with N-donor ligands are widely used as catalysts molecular
switches (SCO) dye-synthesized solar cell (DSSC) As analogs of terpyridine 26-bis(pyrazolyl)pyridines
are widely investigated and there are known a lot of results in coordination chemistry of them [1] Most of
results are related to iron complexes and investigation of spin-crossover
The aim of this work is the synthesis and study of complexes of 3d-transition elements with 26-
bis(pyrazolyl)pyridines A large library of such ligands has been synthesized There are two major branches
of research ndash copper complexes and iron binuclear complexes with 36-bis(pyrazolyl)-1245-tetrazine as
bridging ligand It is common fact that such iron complexes can exhibit two-step spin-crossover transition
from eg HS-HS state to the LS-LS state and also mix-valent species can be stabilized Also for copper bi-
and polynuclear complexes are much interesting due to the possibility of metal-metal interaction
The resulted complexes were investigated by ESR spectroscopy electron spectroscopy mass spectrometry
infrared and Raman spectroscopy their magnetic properties were measured and calculated by quantum-
chemical qualculations For some complexes crystals suitable for X-ray structure analysis were obtained In
the case of iron and cobalt complexes of 26-bis(pyrazolyl)pyridines have a monomeric structure regardless
of counterions and the introduction of additional ligands capable of acting as bridging ligands ndash halide- and
azide- anions Dimeric complexes with bridging ligands could be obtained for copper and nickel There is a
weak ferromagnetic interaction for dimeric copper complexes with the structure [Cu(Cl)(bPzPy)]2(ClO4)2
(Fig 1) calculated coupling constant for which is in agreement with the experimental data For non-
substituted pyrazole one-dimensional chain with perchlorate-bridging was obtained in the first time (Fig 1)
In some cases 1D-chains or more complicated frameworks are formed by hydrogen bonding (Fig 2) [2]
Dinuclear iron complexes has been obtain with 36-bis(pyrazolyl)-1245-tetrazine as bridging ligand and
26-bis(pyrazolyl)pyridines the simple ligands The ground state and possibility of stable mix-valent state
depend on the structure of 26-bis(pyrazolyl)pyridines
The author thanks Prof SI Troyanov Prof YuM Kiselev CandSc VD Dolzhenko VV Korolev and
his students AA Vuhovskiy TD Ksenofontova and AG Gevondyan
1 MA Halcrow Coord Chem Rev 2005 249 2880ndash2908
2 Dolzhenko V D Kurnosov N M and Troyanov S I (2014) Z anorg allg Chem 640 347ndash352
Fig 2 The 1D-chains for complex
[Cu(bPzPy)(H2O)(NO3)2] hydroden bonds are
maked by dotted lines View along the b axis
Fig 1 Structures of
[Cu(Cl)(bPzPy)]2(ClO4)2 (left) and
[Cu(Cl)(bPzPy)(ClO4)] (right)
108
OC47
POLYMER-STABILIZED PALLADIUM NANOPARTICLES AS EFFECTIVE
CATALYSTS OF SELECTIVE HYDROGENATION OF ALKINOLS
LZh Nikoshvili1 VG Matveeva
1 EM Sulman
1 BD Stein
2 LM Bronstein
3
1 - Tver Technical University 170026 Tver Russia
2 - Indiana University Department of Biology IN 47405 Bloomington USA
3 - Indiana University Department of Chemistry IN 47405 Bloomington USA King Abdulaziz
University Jeddah 21589 Saudi Arabia
Selective hydrogenation of unsaturated carbon-carbon bond using Pd nanoparticles (NPs) is of great
importance as widely applicable in synthesis of fine chemicals vitamins and pharmaceuticals One
of the most complicated problems along with achieving of high activity selectivity and stability of
catalytic system is control over the Pd NP size size distribution and morphology [1 2] To achieve
appropriate selectivity traditional industrial catalysts of alkyne hydrogenation require the addition
of modifiers which are not desirable for environment [3-5] Though in the case of terminal
alkynes neither the control of NP morphology [2] nor modification [4] yield the benefits NP size
and stabilizing environment play crucial role and the selectivity problem still exists [5]
Among the organic porous supports for catalyst synthesis hypercrosslinked polystyrene (HPS)
received increased attention due to its high crosslinking degree which can be higher than 100
The unique property of HPS is the ability to swell in different solvents which favors inclusion of
various organometallic compounds in the HPS matrix Besides HPS based catalysts allow control
of the NP formation due to a ldquocagerdquo effect (by limiting the NP size with the pore size) along with
controlling the precursors and reduction conditions
In this work the incorporation of Pd NPs in polymeric matrix of HPS at variation of metal loading
precursor nature and type of polymer (influence of fictionalization) is discussed Series of PdHPS
catalysts was tested in the reaction of selective hydrogenation of 2-methyl-3-butyne-2-ol which is
intermediate of synthesis of fragrant substances and vitamins (E and K) and model compound of
industrially important acetylene alcohols C10 and C15 Physicochemical characterization was
performed via XPS liquid nitrogen physisorption and TEM
Developed catalysts were found to contain Pd NPs with mean diameter of 3-5 nm (Fig 1) and
provide high selectivity (up to 985 at 100 of the substrate conversion) Besides synthesized
HPS-based nanocomposites were highly active in comparison with traditional hydrogenation
catalyst (ie 2(wt)-PdCaCO3) and no leaching of catalytically active compound was observed
Financial support was provided by Seventh Framework Programme of the European Community
(CP-IP 246095-2 POLYCAT) and Ministry of education and science of Russia (contract P1345)
References
1 N Semagina L Kiwi-Minsker Catal Lett 127 (2009) 334
2 L Kiwi-Minsker M Crespo-Quesada Top Catal 55 (2012) 486
3 PW Albers K Moumlbus ChD Frost SF Parker J Phys Chem C 115 (2011) 24485
4 JA Anderson J Mellor RPK Wells J Catal 261 (2009) 208
5 PT Witte PH Berben S Boland EH Boymans D Vogt JW Geus JG Donkervoort Top
Catal 55 (2012) 505
109
OC48
CATALYTIC CARBONYLATION OF OLEFINS ALCOHOLS AND
BENZYL HALIDES IN MOLTEN SALT MEDIUM
OL Eliseev TN Bondarenko AL Lapidus
NDZelinsky Institute of organic chamistry Moscow Russia
Transition metal-catalyzed carbonylation of unsaturated hydrocarbons alcohols and halides is a
direct one-step route to carboxylic acids and esters In presented work we systematically studied
application of some molten salts such as tetrabutylammonium and 1-butyl-3-methylimidazolium
derivatives as a media for these reactions This approach provides a number of unusual possibilities
The most striking result is higher activity of phosphine-free palladium catalyst than that of
ldquotraditionalrdquo Pd-phosphine complexes Bromide-containing molten salts stabilize palladium in the
form of nano-sized suspension as demonstrated by TEM For unsymmetrical olefinic substrates
regioselectivity depends on anion nature in molten salt In particular chloride improves selectivity
to 2-phenylpropanoic acid in carbonylation of styrene Due to high solubility of catalyst in molten
salt it can be used repeatedly by simple extraction of products from reaction mixture with diethyl
ether In dodecene-1 carbonylation ten cycles were carried out without loss of activity and
selectivity Importantly reloading procedure may be performed in air atmosphere Reaction scheme
for the carbonylation of 1-phenylethanol into phenylpropanoic acids is proposed
Hydroxycarbonylation of benzyl halides in molten salt medium proceeds fast in the absence of base
Therefore formation of stoichiometric amount of halide salt may be avoided
110
Posters
111
112
P1
SYNTHESIS OF FLUORESCENT RECEPTORS VIA Pd-CATALYZED
AMINATION OF 6-BROMOQUINOLINE AND
3-BROMOPHENANTHROLINE
AS Abel1 AD Averin
1 AG Bessmertnykh-Lemeune
2 IP Beletskaya
1
1 - MV Lomonosov Moscow State University Department of Chemistry Moscow Russia
2 - Universite de Bourgogne ICMUB Dijon France
Numerous works have been devoted to the design of new fluorescent sensors for various
applications such as clinical toxicology environmental bioorganic chemistry and waste
management [1] To develop optical molecular probes or sensors for toxic metals ruthenium
complexes with ditopic 110-phenanthrolines seem to be an appropriate solution Moreover
aminoquinolines possess good fluorescent properties but have not yet been investigated as a
signaling subunit in chemosensors In this work Pd-catalyzed amination of 6-bromoquinoline (1)
and 3-bromo-110-phenanthroline (2) with linear polyamines 3a-d was investigated to prepare
fluorescent receptors
The fluorescent derivatives of 6-aminoquinoline 4 were synthesized in good yields (up to 62)
using PdBINAP system as catalyst (Scheme) The amination of 3-bromo-110-phenanthroline is
more complicated and Josiphos ligand should be used to obtain 3-amino-110-phenanthrolines 5 in
satisfactory yields (32-36) (Scheme)
Scheme Pd-catalyzed amination of 6-bromoquinoline (1) and 3-bromo-110-phenanthroline (2)
This reaction is a key step in the synthesis of fluorescent receptors 6-8 (Figure) The sensing
properties of receptors 7 and 8 in the presence of various amounts of environmentally-relevant
metal ions were evaluated by UV-vis and fluorescent spectroscopy
Figure Fluorescent receptors for metal ions
Acknowledgements The work was performed in the frames of French-Russian Associated
Laboratory ldquoLAMREMrdquo and financially supported by the RFBR (grant N 12-03-93107) and CNRS
[1] AN Uglov AG Bessmertnykh-Lemeune R Guilard AD Averin IP Beletskaya Russ
Chem Rev 2014 83 196
113
P2
MECHANISM OF CARBON MONOXIDE OXIDATION OVER SUPPORTED
CuO CATALYSTS
YuA Agafonov1 NA Gaidai
1 NV Nekrasov
1 LC Loc
2 N Tri
2 HT Cuong
2 HS Thoang
2
AL Lapidus1
1 - Institute of Organic Chemistry RAS Moscow Russia
2 - Institute of Chemical Technology Vietnam Acad Sci Techn Ho Chi Minh City Vietnam
Supported CuO catalysts with additives of other oxides are effective ones for CO oxidation
Introduction of small amounts of noble metals in these catalysts allows to increase their activity
which can exceed the activity of supported platinum catalysts ndash the most active known ones in CO
oxidation Designing new catalysts for this process requires depth knowledge on the reaction
mechanism This work is devoted to the study of mechanism of CO oxidation over the following
supported on -Al2O3 catalysts 10 (wt) CuO (CuAl) 10 CuO+20 CeO2 (CuCeAl) 10
CuO+10 Cr2O3 (CuCrAl) without and with addition of Pt The content of Pt varied in the range
of 005 ndash 03 wt The following physico-chemical methods were used for catalyst investigation
BET N2-Adsorption XRD TPR SEM EDS and IR-CO adsorption There are the surface data of
studied catalysts in Table
It is seen that the Cr Ce and Pt
enhanced the reducibility of copper
catalysts what expressed in the decrease
of the reduction temperature and the
increase of the reduction extent (the
reducibility of catalysts CuAl and
CuCeAl was increased in 25 ndash 3 times)
It was shown that the optimal Pt content
is 01 With this amount of Pt catalyst
PtCuCeAl was capable to convert
completely CO to CO2 at 110oC
(without Pt - at 125oC) The process
mechanism was studied by unstationary
response method Relaxation curves
describing a transition of the system to a
new steady state were obtained by a
jump change of the corresponding concentrations The residence time defined as the ratio of the
reaction system volume to the flow rate was 2-5 times lower than the turnover time It is meant that
the observed transition phenomena were associated with the intrinsic processes It was shown that
Pt weakened the interaction of active phase which resulted in an increase of the reaction rate The
initial substances participated in the reaction in adsorbed state the most part of the surface was
occupied by oxygen over all the catalysts Ce was facilitated the mobility of oxygen Pt was
increased the bond strengh of CO O2 and CO2 with the surface of catalysts Not only adsorbed
oxygen but lattice oxygen took part in the reaction but the last oxygen in less extent The change of
introduced glass filler in the reactor showed that reaction of CO oxidation proceeds mainly through
heterogeneous mechanism the share of homogeneous mechanism does not exceed 15 It was
shown that CO and O2 adsorption were quick steps one intermediate compound was formed in
slow step of the process The overall step-scheme of CO oxidation was proposed over studied
catalysts The work is supported by RFBR (13-03-93001_Viet_a) and NAFOSTED grant 10403-201260
Catalysts SBET
m2g
dCu
nm
γCu
Tmax
C
KRed
Oxide Catalysts
CuAl 1770 119 131 375 130
CuCrAl 1660 155 100 355 284
CuCeAl 670 - - 321 176
Pt-containing oxide catalysts
01PtCuAl 959 116 134 274 367
02PtCuAl 951
005PtCuCrAl 892 188 83 308 299
01PtCuCeAl 801 352 44 255 458
Table Surface characteristics of the studied catalysts
specific surface area (SBET) crystal size of Cu (dCu)
dispersion of Cu (γCu ) maximum reduction
temperature (Tmax) and extent of reduction for ions
Cu2+
(KRed )
114
P3
EFFICIENT CATALYTIC HYDRODEOXYGENATION OF
UNPROTECTED CYCLIC IMIDES TO CYCLIC AMINES BY
HETEROGENEOUS CATALYSIS
AM Maj I Suisse F Agbossou-Niedercorn
University Lille Nord de France UCCS UMR 8181 CNRS ENSCL C7 CS90108 59652 Villeneuve
d Ascq Cedex France
Cyclic amines comprising fused saturated N-heterocycles are valuable synthetic intermediates They
are found in numerous drug candidates such as bicifadine cytisine gliclazide or telaprevir to name
just a few (Figure 1) The catalytic hydrogenation of imides appears to be the most elegant and
promising reaction to produce properly and efficiently such amines Since the reaction might
potentially lead to several compounds it needs to be controlled by an appropriate catalyst which
has to perform selectively two successive reductive cleavages of the C=O functionalities without
breaking the cycle
Figure 1 Bioactive cyclic amines
As part of our ongoing interest for the application of catalytic hydrogenation in the preparation of
cyclic amines[1]
we became interested in the synthesis of fused N-heterocycles Herein we report
on the first efficient total reduction of nitrogen-unsubstituted cyclic imides in the presence of
heterogeneous catalysts generated in situ from rhodium and molybdenum carbonyls (Scheme)
Various substrates could be reduced with high selectivities and yields (both up to 100) Platinum
catalysts proved also efficient to hydrogenate some cyclic imides In addition all catalysts could be
recycled at least three times without significant loss of activity Finally hydrodeoxygenation of a
model cyclic imide was successfully performed on a gram scale[2]
References
[1] a) Maj A M Suisse I Meacuteliet C Agbossou-Niedercorn F Tetrahedron Asymmetry 2010
21 2010 b) Maj A M Suisse I Meacuteliet C Hardouin C Agbossou-Niedercorn F
Tetrahedron Lett 2012 53 4747 c) Maj A M Suisse I Hardouin C Agbossou-
Niedercorn F Tetrahedron 2013 69 9322
[2] Maj A M Suisse I Pinault N Robert N Agbossou-Niedercorn F ChemCatChem
accepted
HN
pTol
N
O
NH
NH
NH
S
OOO
N
O
HN
NHO
N
O
N
N
H
H
NHO O
NHO
Bicifadine Cytisine Gliclazide Telaprevir
N
O
O
H( )n
n = 0 or 1
N
O
H( )n N H( )nN
OH
H( )n+ +catalyst
PH2 T
solvent
up to 100 yield
115
P4
REACTIONS OF N-ALKYLHALOGENALDIMINES WITH OO-
DIALKYDITHIOPHOSPHORIC ACIDS
NG Aksenov RA Khairullin MB Gazizov RN Burangulova
Kazan National Research Technological University Department of Organic Chemistry Kazan
Russian Federation
We found that direction of interaction of N-alkyl-2-halogenaldimines (1-2) with ОО-
dialkyldithiophosphoric acids (3) mainly depends on the nature of halogen Reaction between ОО-
dialkyldithiophosphoric acids (3) and N-alkyl-2-chloroaldimines (1) was first studied by dynamic 1Н
13С and
31Р NMR in the temperature intervals from -60 degC to 25 degС It was found that reaction
proceeds in two steps At first step which proceeds at -60 degС the protonation of imine nitrogen
occurs and intermediate iminium salts are formed ndash ОО-dialkyldithiophosphates N-
alkylchloroaldiminium (4) At the second step which is observable at -5-0 degС the chlorine atom is
substituted by ОО-dialkyldithiophosphate group The final products of the reaction are chlorides of
N-alkyl-2-ОО-dialkyldithiophosphatopropaniminium (5) We propose that salt (4) is transfromed
into product (5) through the intermediacy of salt (6) with delocalized azaallyl dication as a result of
heterolytic dissociation of the bond tertiary carbon-chlorine
Synthetic result of the reaction of dithioacid (3) with N-alkyl-2-bromoaldimine (2) is completely
different ndash as major products were obtained phosphorylsulfide (7) and iminium salt of unsubstituted
aldimine (8) Thus we for the first time discovered the reaction of reduction of organic bromine
derivative (2) by ОО-dialkyldithiophosphoric acid At temperatures -80 ndash -70 degС 31
Р NMR
spectroscopy allowed to detect the formation of intermediate salt (9 δ 108 ppm)
The work is supported by RFBR and the Government of Tatarstan project 13-03-7098_p
povolzhe _а2013 and Ministry of education and Science (task 201456 within the framework
of basic part of stat task)
116
P5
METAL-FREE TRANSANNULATION REACTION OF INDOLES WITH
NITROSTYRENES SIMPLE PRACTICAL SYNTHESIS OF QUINOLINE
DERIVATIVES
AV Aksenov1 NA Aksenov
1 IV Aksenova
1 AN Smirnov
1 M Rubin
2
1 - Department of Chemistry North Caucasus Federal University Stavropol Russian Federation
2 - Department of Chemistry University of KansasLawrence USA
A convenient metal-free method for preparation of a large variety of 3-aryl- and 3-alkylsubstituted
2-quinolones 4 as well as 23-disubstituted quinolines was proposed This approach involves
previously unknown transannulation of 2-substituted indoles 1 in the reaction of β-nitrostyrenes 2 in
polyphosphoric acid The method is based on the ring-expansion of the pyrrole cycle in indoles
upon attack of amphyphilic reagents at the enamine double bond
N
R2
R1
R3
N+
O
ON
R2
R1
R3
N O H
O P( O )( O H )2
P P A
H+
H+
N
R2
R1
R3
O
NH
O H
OH2
N+
O P( O )( O H )2
N O H
R2
R3
R1
ON
N
R2
R1
R3
O P( O )( O H )2
ON H
N
R2
R1
R3
O P( O )( O H )2
R3
N H
O P( O )( O H )2
N
R2
O
R1
R3
N
N H
R1
OR2
OP
O
O H
OH
N
R1
R3
O
N
P
O
O H
O H
R2
O
N
R1
O
NH
+O
P
O
O
R2
R3
H+
N O
R3
R1
R2
NH
O P( O )( O H )2
+
2
1
-
+3
+
4
R
1= H Me R
2= Ph Me R
3= Ph 4-MeOC6H4 4-iPr-C6H4 34-Me2C6H3 4-EtOC6H42-FC6H4 34-
Cl2C6H3 3-BrC6H4 n-Pr
Introduction of an alkyl substituent into β-position of β-nitrostyrene 6 renders formation of
quinoline 7 as major product The mechanism of this transformation is identical to the one shown
above but includes elimination of water and aromatization at the last step
NH
R2 N
+R3
O
O N
R3
NH2
R2
O
+ +
1 6 7 5 R
2= Ph Me R
3= Ph Ph
Convenient and general metal-free approaches to 3-aryl and 3-alkyl-substituted 2-quinolones as
well as to 23-disubstituted quinolines were developed which included the previously unknown
process of transannulation of 2-substituted indoles in the reaction with β-nitrostyrenes in
polyphosphoric acid The reaction was also efficiently combined into a cascade with a Fisher indole
synthesis Unlike most other known methods the described protocol utilizes readily available
starting materials Unique properties of PPA serving as a mild proton donor source of efficient
leaving group (or temporary protecting group) water scavenger and high boiling solvent makes it
an ideal media for the described transformation
This work was carried out with financial support from the RFBR (grant 13-03-003004)
117
P6
MECHANOCHEMICAL SYNTHESIS OF CHROMIUM CARBOXYLATES
AND THEIR CATALYTIC PROPERTIES IN ETHYLENE TRIMERIZATION
KA Alferov1 LA Petrova
2 VD Makhaev
2 GP Belov
1
1 - Institute of Problems of Chemical Physics RAS Department of Polymers and Composite
Materials Chernogolovka Russian Federation
2 - Institute of Problems of Chemical Physics RAS Department of Functional Inorganic Materials
Chernogolovka Russian Federation
Selective synthesis of individual alpha olefins (1-butene 1-hexene 1-octene) is an urgent problem
because these compounds are widely used for the production of ethylene copolymers plasticizers
lubricants etc [1 2] One of the most efficient systems for ethylene trimerization is a system based
on chromium tris(2-ethylhexanoate) (Cr(EH)3) 25-dimethylpyrrole and organoaluminum
compounds Methods for the synthesis of Cr(EH)3 based on reactions in solutions are quite
laborious and lingering The products obtained by the methods are sticky and unhandy The
operations for the isolation and purification of the product complicate its production [3 4 5]
Nowadays green chemistry seems as a very promising research area so the processes of solvent-
free solid reactant interactions attract much attention We have developed a method for the
synthesis of Cr(EH)3 based on the solvent-free mechanochemical interaction of solid CrCl3 and
NaEH with subsequent heating of the reaction mixture [6] Physicochemical properties of the
reaction products and mechanically activated CrCl3-NaEH mixtures at different CrCl3NaEH ratios
were investigated by IR-spectroscopy XRDA and DCS The solid phase interaction of CrCl3 and
NaEH occurs in two main stages 1) the reagents mixture mechanical activation resulting in their
dispersion and mixing at the molecular or cluster level and 2) thermally initiated exothermic
interaction of the activated reactants to give the final products The use of the method makes it
possible to shorten the process duration appreciably
The obtained reaction mixtures and isolated Cr(EH)3 as well as commercially available Cr(EH)3 (8-
10 wt in mineral spirits) were tested as components of the Cr(EH)325-
dimethylpyrroleAlEt3CCl4 catalytic system for ethylene trimerization The productivity and
selectivity of the catalyst based on Cr(EH)3 synthesized by the mechanochemical method were
similar to the results obtained for the commercial Cr(EH)3 Moreover reaction mixtures produced
directly after the synthesis of Cr(EH)3 also form an active catalyst for ethylene trimerization
Syntheses differed in the time of mechanochemical activation (1-4 h) and reagent ratio
(NaEHCrCl3 = 23 ndash 39) were also performed The catalytic systems based on thus obtained
reaction mixtures demonstrated close values of productivity (11-13 kg(gCrmiddoth)) and selectivity (1-С6
= 82-85 wt C8+ = 13-15 wt PE = 01-03 wt) in ethylene to 1-hexene trimerization
The study was in part financially supported by the Russian Foundation for Basic Research (project
no 12-03-00974-a) and by the Presidium of the Russian Academy of Sciences Basic research
Program 3
[1] Dixon JT Green MJ Hess FM Morgan DH J Organomet Chem 689(23) 3641-3668
(2004)
[2] McGuinness D S Chem Rev 111(3) 2321-2341 (2011)
[3] Briggs JR US 466838 (Union Carbide Corporation) March 14 1986
[4] Knudsen RD et al US 20070043181 A1 (Chevron Phillips Chemical Company) August 19 2005
[5] Sydora OL et al US 20130150642 A1 (Chevron Phillips Chemical Company) December 12
2011
[6] Rus Patent Application 201315651220(088111) (IPCP RAS) December 20 2013
118
P7
EFFECT OF CHEMICAL STRUCTURE OF VIOLOGEN-DERIVATIVES AS
AN ARTIFICIAL CO-ENZYME ON THE CARBON DIOXIDE REDUCTION
ACTIVITY OF FORMATE DEHYDROGENASE
Y Amao1 S Ikeyama
2
1 - Osaka City UniversityAdvanced Research Institute for Natural Science and Technology
OsakaJapan
2 - Osaka City UniversityGraduate School of Science OsakaJapan
Many studies on electro-catalyzed CO2 reduction have been performed using specific electrode
materials On the other hand studies on CO2 fixation also have investigated photocatalysis on
semiconductors such as titanium dioxide silicon carbide and strontium titanate However these
systems use ultraviolet irradiation and the total reaction is low yield whereas highly efficient CO2
fixation system using visible light is more desirable We previously reported a system for visible
light-induced methanol synthesis from CO2 with the system formate aldehyde and alcohol
dehydrogenases and methylviologen (MV2+
) photoreduction by the visible light photosensitization
of water soluble zinc porphyrin in the presence of an electron donor in aqueous media On this
system the reduced form of methylviologen (MV+
) is used as an artificial co-enzyme for these
dehydrogenases To improve the yield for methanol production from CO2 conversion of CO2 to
formic acid with formate dehydrogenase (FDH) and reduced formed viologen is most important
step
In this work some artificial co-enzymes with 44rsquo- bipyridine skeletons as shown in Figure 1 are
synthesized and effect of chemical structures of
artificial co-enzymes on the activity of the reduction
of CO2 to formic acid with FDH are investigated
The conversion of CO2 to formic acid with FDH and
one-electron reduced form of artificial co-enzyme
was carried out as following method The sample
solution containing 30 micromol of artificial co-enzyme
57 mmol of sodium dithionate and FDH (10 units)
in 36 ml of CO2 saturated sodium pyrophosphate
buffer (pH 74) at 305 ˚C for 1 min The formic acid
concentration produced is measured by ionic chromatography
By using MV2+
as the reference the formic acid production increased by using cationic artificial co-
enzymes (H2NH2CH2C-V-CH2CH2NH2 and CH3-V-CH2CH2NH2) On the other hand the HCOOH
production decreased by using anionic co-enzymes (HOOCH2C-V-CH2COOH and CH3-V-
CH2COOH) The production of formic acid in this reaction depends on chemical structures of
artificial co-enzymes Among the artificial co-enzymes H2NH2CH2C-V-CH2CH2NH2 has high
affinity for FDH compared with the other compounds
Figure 1 Chemical structures of viologen-derivatives as artificial co-enzymes for formate dehydrogenase
119
P8
Cu(I)-CATALYZED ARYLATION OF BIOLOGICALLY ACTIVE
DI- AND POLYAMINES
AD Averin MV Anokhin SP Panchenko IP Beletskaya
MV Lomonosov Moscow State University Department of Chemistry Moscow Russia
Di- and polyamines like putrescine cadaverine spermidine and spermine were chosen for the
studies of their Cu(I)-catalyzed NNrsquo-diarylation for the synthesis of new compounds with diverse
biological activity Arylation was carried out using iodobenzene 4-fluoroiodobenzene 4-
(trifluoromethyl)iodobenzene and 4-iodobiphenyl The reactions of butane-14-diamine were
successfully catalyzed with either CuIL1 (L1 = L-proline) or CuIL2 (L2 = 2-
isobutyrylcyclohexanone) systems while pentane-15-diamine demonstrated better results with
CuIL2 system Cs2CO3 was taken as a base in all cases
Selective N
1N
3-diarylation of triamine and N
1N
4-diarylation of tetraamine turned to be a more
complicated task and target compounds were obtained in moderate yields using CuIL2 catalytic
system
Acknowledgement The work was financially supported by the RFBR grant N 12-03-00796
120
P9
NITRATING AND NITROSATING REAGENTS IN NOVEL
HETEROCYCLIZATION REACTIONS READY ACCESS TO HIGHLY
SUBSTITUTED PYRIMIDINE AND ISOXAZOLE DERIVATIVES
EB Averina KN Sedenkova DA Vasilenko TS Kuznetsova NS Zefirov
Lomonosov Moscow State University Department of Chemistry
Recently we have elaborated novel synthetic approaches to five- and six-membered N- and NO-
heterocycles basing on the heterocyclization of electrophilic alkenes or three-membered carbocycles
under the treatment with nitrating or nitrosating reagents
The reaction of tetranitromethane with electrophilic alkenes in presence of triethylamine was found
to afford 5-nitroisoxazoles 1 ndash highly reactive and versatile compounds which may be used as
precursors of diverse functionalized compounds [1] Employing the reduction of nitroisoxazoles 2
we suggested the regioselective method of synthesis of 5-aminoisoxazoles 2 that was used to
accomplish a structure design of biologically active compounds The series of compounds 2 was
obtained in good yields (50-90) and their antiviral activity was investigated
A series of previously unknown 4-fluoropyrimidine 1-oxides 4 was obtained via three-component
heterocyclization involving gem-bromofluorocyclopropanes 3 nitrosating or nitrating agent and
organic nitrile [2] Preparative method of synthesis of 4-fluoropyrimidines 5 from corresponding N-
oxides under the treatment with PCl3 was elaborated
F
Br RCN
R1
R2
R1
R2 N
N
F
O
RR1 R2
CBrF
R1
R2 N
N
F
R
[NO+]
RR1R2 Alk Ar
[NO+] NOBF4
NO2BF4 NO2OTf
3 4
5
NO
EWG
NO2
R2
EtOH
C(NO2)4 -Et3N
PCl3
NO
EWG
NH2
R2
SnCl2
2
R1 = EWG (C(O)R
CO2R P(O)(OEt)2
NO2 CO2R)
R2 = H Alk
1
4-Fluorosubstituted pyrimidine N-oxides 4 and pyrimidines 5 demonstrate high reactivity in
aromatic nucleophilic substitution with various O- N- P-nucleophiles In particular a series of 4-
aminopyrimidines and pyrimidine N-oxides potent as compounds with antiviral activity was
obtained via this reaction
In conclusion simple and efficient synthetic methods allowing polyfunctionalized isoxazoles
pyrimidines and pyrimidine N-oxides including those with valuable properties from readily
available starting materials were developed
We thank the Russian Foundation for Basic Research (Projects 14-03-31989-mol_а 14-03-00469-
a) and Presidium RAS (program 8P) for financial support of this work [1] (a) YA Volkova EB Averina YK Grishin P Bruheim TS Kuznetsova NS Zefirov J Org Chem
2010 75 3047-3052 (b) EB Averina YA Volkova YV Samoilichenko YK Grishin VB
Rybakov AG Kutateladze ME Elyashberg TS Kuznetsova NS Zefirov Tetrahedron Lett 2012
53 1472ndash1475 [2] (a) KN Sedenkova EB Averina YuK Grishin AG Kutateladze VB Rybakov
TS Kuznetsova NS Zefirov J Org Chem 2012 77 9893ndash9899 (b) KN Sedenkova EB Averina
YuK Grishin TS Kuznetsova NS Zefirov Tetrahedron Lett 2014 55 483ndash485
121
P10
TRANSFER HYDROGENATION OF ACETOPHENONE OVER BIS-IMINE
RHODIUM(I) COMPLEX DFT STUDY
NM Badyrova1 Z Lin
2 LO Nindakova
1
1 - Irkutsk State Technical University Physical and Technical Institute Irkutsk Russia
2 - The Hong Kong University of Science and Technology Department of Chemistry Hong Kong
(P R China)
There are two reaction mechanisms for asymmetric transfer hydrogenation reactions of ketones over
a diamine rhodium(I) complex leading to optically active secondary alcohols a stepwise process
through an intermediate hydride complex derived from an alkoxy complex via -hydride
elimination and a concerted process where the hydrogen is directly transferred from the alkoxy
complex to the coordinated substrate [1]
Here we investigated mechanism of hydrogen transfer reaction (Scheme 1) from 2-propanol to
acetophenone over a bis-imine-rhodium(I)-chloride complex with optical active bisndashimine ligand
RR-1 on the basis of DFT theoretical calculations
Scheme 1
Based on the mechanism proposed by Guiral et al [1] we designed a catalytic cycle (Scheme 2)
This cycle starts with the hydride complex 1 The first step is reversible dissociation of a Rh-N
bond in the 18-electron hydride complex leading to a 16-electron intermediate (the hydride complex
2) From 2 there are two possible pathways to achieve hydride transfer to acetophenone an external
pathway vial 3a and an internal pathway via 3b (Scheme 2) Both the two hydride transfer pathways
give the alkoxy complex 4 which leads to 5 after with a metathesis with 2-propanol to release the
product molecule Next step involves -H elimination to give 6 followed by release of the side-
product (acetone) to regenerate the starting hydride complex 1
Scheme 2
N N
N NRh
H
N N
N
NRh
O
CH
H3CPh
N N
N
NRh
O
CH
H3CCH3
N N
N
NRh
H
O
C
H3C CH3
N N
N
NRh
H
N N
N
NRh
H
OC
CH3
Ph
N N
N
NRh
H O
CH3C
Ph
(CH3)2CHOH
(CH3)PhCHOH(CH3)2CO
1
2
3a
3b
4
56
Geometry optimizations of all species have been performed by means of the DFT M06 hybrid
method [2] The 6-31G(d) basis set was chosen to describe C N O H atoms and the LanL2DZ
basis set was used for Rh All of the calculations were performed with the Gaussian 09 program [3] 1 Guiral V Delbecq F Sautet P Organometallics 2000 19 1589-1598
2 Zhao Y Truhlar D G Theor Chem Account 2008 120 215-241
3 Frisch M J et al Gaussian 09 Revision A1 Gaussian Inc Wallingford CT 2009
122
P11
RHODIUM(II) CATALYZED REACTIONS FOR SYNTHESIS OF NOVEL
AND DIVERSE FURO[23-D]PYRIMIDINEDIONES AND
THIOXOFURO[23-D]PYRIMIDINEONES
ER Baral KB Somai Magar YR Lee
School of Chemical Engineering Yeungnam University Gyeongsan 712-749 Republic of Korea
Furopyrimidines the derivatives of pyrimidine and analog of purine have been demonstrated to
have antimalarial antifolate antitumor antiviral antibacterial and antifungal and antihypertensive
properties1-2
Accordingly several methods have been devised to synthesize furopyrimidines3-4
The
general methods for the synthesis of furo[23-d]pyrimidinediones by ceric ammonium nitrate
mediation involving ionic (non-carbenoid) mechanism is limited with the substrate scope in terms
of olefins and alkynes with low yields5 while three component reactions of NNrsquo-dimethylbarbituric
acid with benzaldehydes and isocyanides provided 23-disubstituted furans6 However there is a
need for more convenient and efficient synthetic methods for the preparation of furo[23-
d]pyrimidinedione derivatives and in particular the synthesis of thioxofuro[23-d]pyrimidinedione
derivatives has not been reported to date
In this conference we present the rhodium (II)-catalyzed reactions of cyclic diazo compounds
derived from barbituric acid or thiobarbituric acid with arylacetylenes and styrenes These reactions
provide a rapid synthetic route to the preparation of a variety of novel and diverse furo[23-
d]pyrimidine-24-diones 2-thioxodihydrofuro[23-d]pyrimidin-4-ones dihydrofuro[23-
d]pyrimidine-24-diones and 2-thioxotetrahydrofuro[23-d]pyrimidin-4-ones
N
N
O
O
N2R
R
X
X=O SR=Me Et
Y
Rh2(OPiv)4
N
N
O
R
R
X O Y
Y
Rh2(OPiv)4
N
N
O
R
R
X O Y
PhFrt - 60 oCtoluene
reflux
References
1 G Jaumlhne H Kroha A Muumlller M Helsberg I Winkler G Gross T Scholl Angew Chem Int
Ed Engl 1994 33 562-563
2 Q Dang Y Liu M D Erion J Am Chem Soc 1999 121 5833-5834
3 A Sniady M D Sevilla S Meneni T Lis S Szafert D Khanduri J M Finke R Dembinski
Chem Eur J 2009 15 7569-7577
4 A Sniady A Durham M S Morreale A Marcinek S Szafert T Lis K R Brzezinska T
Iwasaki T Ohshima K Mashima R Dembinski J OrgChem 2008 73 5881-5889
5 K Kobayashi H Tanaka K Tanaka K Yoneda Synth Commun 2000 30 4277-4291
6 M B Teimouri R Bazhrang Bioorg Med Chem Lett 2006 16 3697-3701
123
P12
DUAL REACTIVITY OF NTROARENES IN [4+2]-CYCLOADDITION
REACTIONS
MA Bastrakov AM Starosotnikov SA Shevelev
ND Zelinsky Institute of Organic Chemistry RAS Laboratory of Nitrogen-containing Aromatic
Compounds Moscow Russia
[4+2]-Cycloaddition is one of the fundamental protocols for the construction of a new ring which
accompanies the formation of two bonds This reaction is known for nitroalkenes1a
as well as for
few highly electrophilic (low aromatic) benzoazoles1b-c
These compounds readily undergo Diels-
Alder reactions at C-C double bond activated by the nitro group Also they form anionic σ-adducts
with very weak nucleophiles1b
As a part of our research on highly electrophilic heterocyclic systems we have found that 46-
dinitroanthranil reacts with dienes and nucleophilic dienophiles in mild conditions2
Moreover we have proposed methods for the synthesis of new policyclic heteroaromatic
compounds on the nitroarenes basis consisting in annelation of a furoxan ring to different
dinitrobenzoazoles and azines3 Some of these compounds readily undergo [4+2]-cycloaddtition
with dienes and dienophiles
This work was supported by the Russian Foundation for Basic Research Projects No 13-03-00452
14-03-31508 mol_a and Grant of the President of the Russian Federation for State Support to young
Russian scientists Grant MK-359920133
1 (a) SE Denmark A Thorarensen Chem Rev 1996 96 137 (b) S Lakhdar R Goumont T
Boubaker M Mokhtari F Terrier Org Biomol Chem 2006 4 1910 (c) S Kurbatov R
Goumont S Lakhdar J Marrot F Terrier Tetrahedron 2005 61 8167
2 AM Starosotnikov MA Leontieva MA Bastrakov AV Puchnin VV Kachala IV
Glukhov SA Shevelev Mendeleev Commun 2010 20 165
3 MA Bastrakov AM Starosotnikov IV Glukhov SA Shevelev Russ Chem Bull Int Ed
2009 58 426
124
R2NH
COOH
N
O
O
R
R = C2H5 (3) n-C3H7 (4) n-C4H9 (5)
(3 4 5)
COOH
O
O
OR +
R = H (1) CH3 (2)
R = CH3
135oC
R = H
COOH
N
O
O
R
COOH
NR2
COOH
O+
(6-8) (9 10)
R = C2H5 (6 9) n-C3H7 (7 10) n-C4H9 (8) The exact structure of regioisomer is not established
(1 2)135oC
COOH
N
O
OR
R+ +
R = CH3 C2H5 R = H CH3
R
HN
OH
COOH
N
O
OR
OH
P13
UNEXPECTED FORMATION OF N-ALKYLIMIDES IN REACTION OF
MALEOPIMARIC AND CITRACONOPIMARIC ACIDS WITH
SECONDARY AMINES
MP Bei1 AP Yuvchenko
1 AV Baranovsky
2
1 - The Institute of Chemistry of New Materials 36 FSkoriny st Minsk 220141 Belarus
2 - The Institute of Bioorganic Chemistry 52 Kuprevich st Minsk 220141 Belarus
The Diels-Alder reaction of levopimaric acid with active dienophiles produces adducts (maleo- fumaro-
quinopimaric acids) which are useful precursors in the synthesis of chiral ligands terpenoquinones
biologically active compounds Recently we have reported the synthesis of isomer of citraconopimaric acid
(2) an analog of well-known maleopimaric acid (1) bearing methyl group at C-151
The method includes
preparation of the adduct of pine rosin with citraconic anhydride (formed in situ from itaconic acid) followed
by recrystallization of the product from carbon tetrachloride and benzene
We have initiated the investigation of the reaction of citraconopimaric acid (2) with some secondary aliphatic
amines in order to study the steric influence of the CH3 group at C-15 of the acid (2) on regioselectivity of
anhydride ring opening by nucleophilic agents
It was established that the heating of citraconopimaric acid (2) solution in diethylamine dipropylamine in
autoclave dibutylamine at 135ordmC for 30h leads to the formation of N-ethyl- N-propyl- N-butylimides of
citraconopimaric acid (3minus5) Unlike citraconopimaric acid (2) reactions of maleopimaric acid (1) with
diethyl- dipropylamine at 135ordmC gave N-ethyl- N-propylimides of maleopimaric acid (6 7 yields 60minus80)
and amidodiacids (9 10 yields 10minus15) and the reaction with dibutylamine gave only maleopimaric acid
N-butylimide (8)2
The formation of N-alkylimides (3minus8) in the above transformations could be result of a thermal degradation
of intermediate amidoacids giving stable cyclic imides Would this assumption be true the formation of
mixture of two imides should be observed in the reaction of acids (1 2) with unsymmetrical secondary
amines Thus when acids (1 2) were treated with methyl- or ethyl-(2-hydroxyethyl)amine the formation of
a mixture of two imides indeed was observed2
[1] MP Bei AP Yuvchenko Patent of the Republic of Belarus 13646 2009
[2] MP Bei AP Yuvchenko AV Baranovsky Proceed Nat Acad Sci Belarus 2013 N 4 104
125
P14
SYNTHESIS OF TRYPTAMINES FROM CYCLOPROPYLKETONES
ARYLHYDRAZONES AND THEIR BIOLOGICAL STUDIES
AYu Belyy1 RF Salikov
2 YuV Tomilov
2
1 - Higher Chemical College of Russian Academy of Sciences
2 - N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences
Tryptamine derivatives are psychoactive compounds and are widely used as 5-HT agonists We
have found that cyclopropyl methyl ketone hydrazones rearrange into a mixture of
tetrahydropyridazines and tryptamines the best yield of tryptamine being observed in the case of
generated in situ bromophenylhydrazone The rearrangement of cyclopropyl ketones with a bulky
group in most cases gives tetrahydropyridazines exclusively
The tryptamine derivatives obtained demonstrated their antitumor activity against human
neuroblastoma cell line SH-SY5Y The best result was shown by 2-methyl-5-bromotryptamine
(IC50 = 506 microМ) with the therapeutic index of 4 determined from the toxicity against human
embryonic kidney cells (HEK 293)
In order to investigate the biological activity of this interesting class of compounds we derived the
tryptamines in three different ways substitution of bromine indole nitrogen alkylation and primary
amine nitrogen The biological studies are under performance
126
P15
DEHYDROGENATION OF LOW ALIPHATIC ALCOHOLS ON COPPER
SUPPORTED STRUCTURED CATALYST
DA Bokarev1 EA Ponomareva
2 EV Egorova
2
1 - ND Zelinsky Institute of Organic Chemistry RAS Moscow Russia
2 - Lomonosov Moscow State University of Fine Chemical Technologies Moscow Russia
The important direction of the chemical industry development is engineering of new alternative
manufactures based on renewable sources of raw materials These materials could be methanol and
ethanol especially applied for synthesis of methylformiat and acetaldehyde respectively
2CH3OH rarr HCOOCH3+2H2
C2H5OH rarr CH3CHO +H2
To realize the process of dehydrogenation with high technical parameters new catalytic systems
must be worked out Recently new classes of heterogeneous catalysts based on structured carbon
fibers were developed They possess a number of advantages - homogeneous distribution of a
stream low pressure drop Moreover fibers structured catalysts offer flexibility and endless forms
that allow using them in reactors of a various constructions
It was shown that 5 wt of copper supported by impregnation appeared to be optimal in the
process of alcohol dehydrogenation Compared to powder and granular carbon materials used
earlier catalysts based on structural carbon fibers showed higher activity and selectivity due to
better distribution of active component on the surface of the carrier (fig1)
Fig 1 Distribution of copper particles on the surface of carbon structured fiber (left) and granular
carbon material Sibunit (right)
Thus application of structured carbon fibers as a support of copper catalytic system leads to
increase of activity in comparison with known literature data That allows to make a conclusion
about appropriateness of using it in the process of dehydrogenation of low aliphatic alcohols
Activity ndash 126 gMeOHgCuh and 237 gEtOHgCuh
Activity ndash 24 gMeOHgCuh and 68 gEtOHgCuh
127
P16
ARYLAMINATION OF 137-TRIAZAPYRENES
IV Borovlev OP Demidov NA Saigakova GA Amangasieva
North Caucasus Federal University Department of Chemistry Stavropol Russia
In our previous reports we have shown that 137-triazapyrene displays peculiar properties due to
the unique fusion of the carbocyclic and heterocyclic rings Specifically these properties include the
unusual ease of oxidative nucleophilic substitution of hydrogen such as amination [1] and
alkylamination [2] which proceed in aqueous media The aim of this work is the synthesis of
arylamino derivatives of this heterocycle In spite of a common mechanism the conditions
mentioned above are not suitable for arylamination reaction due to the low nucleophilicity of aryl
amines and their high sensitivity towards oxidation This is why SNH-arylamination reactions are
still rare
We have found that the interaction of 137-triazapyrenes 1 with an excess of sodium arylamides
obtained in situ in absolute DMSO proceeds at room temperature to form the 6-aryl(hetaryl)amino-
137-triazapyrenes 2 in 32-97 yields It was shown that the decisive factor for rearomatization of
σH-adducts is crucial access to the air oxygen
NN
N
R
X
NN
N N H A r
R
X
1 A rN H - N a +
D M S O R T O2
1 2
2 H2O
R = H Me X = H Ar NR2
Under the same conditions (DMSO room temperature) the reaction of the rather accessible 68-
dialkoxy-137-triazapyrenes 3 with sodium aryl amide has resulted to a product of nucleophilic
ipso substitution of one of the two RO groups - 6-alkoxy-8-aryl(hetaryl)amino-137-triazapyrenes
4
NN
NR O O R
NN
N N H A rA r N H
NN
NR O N H A r
1 A rN H - N a +
D M S O R T
3 5
2 H2O
1 A rN H - N a +
re flu x in g to lu en e
2 H2O
4 R = Me Et
Products of double ipso substitution ndash 68-bis(aryl(hetaryl)amino)-137-triazapyrenes 5 were
synthesized by refluxing of the compounds 3 with excess of the sodium arylamides in toluene for a
long time Consecutively replacing one methoxy group in 68-dimethoxy-137-triazapyrene in
DMSO and the second - in toluene we obtained asymmetrically substituted diamine - 6-
phenylamino-8-(pyridin-4-ylamino)-137-triazapyrene
This project received financial support from the Ministry of Education and Science of the Russian
Federation in the framework of the State Assignment to the Higher Education Institutions
41412014K
[1] O P Demidov I V Borovlev N A Saigakova O A Nemykina N V Demidova and S V
Pisarenko Khim Geterotsikl Soedin 142 (2011) [Chem Heterocycl Compd 47 114 (2011)]
[2] I V Borovlev O P Demidov N A Saigakova S V Pisarenko O A Nemykina J
Heterocycl Chem 48 No 5 1206 (2011)
128
P17
SUSTAINABLE APPROACHES FOR ORGANIC SYNTHETIC PROCESSES
LC Branco K Zalewska G Carrera MN Da Ponte
REQUIMTE Departamento de Quнmica Faculdade de Ciкncias e Tecnologia Universidade Nova
de Lisboa 2829-516 Caparica Portugal
For many synthetic approaches the incorporation of CO2 as alternative reagent or green solvent can
improve significantly the efficiency (yields purity reaction conditions) for several organic
processes In recent years the use and capture of Carbon Dioxide (CO2) became a hot research topic
including their application for organic and pharmaceutical chemistry1 The possibility to use carbon
dioxide as useful reagent for different synthetic approaches or supercritical CO2 for efficient
extraction and separation processes has been reported1
The combination of ionic liquids and supercritical fluids has been reported for many organic
transformations in particular catalytic reactions2 The possibility to use scCO2 in order to extract the
pure products without IL or catalyst contamination is one of the advantages for these processes
Several publications proof the advantages for ILs and scCO2 combinations in order to recycle the
catalytic media during many reaction cycles without loss of efficiency
In this communication we described the applicability of carbon dioxide approaches in two different
organic synthetic processes3
a) The use of CO2 as reagent for the preparation of reversible chiral and non-chiral carbamate
salts by the reaction with different amines (eg primary alkyl and aryl amines or polyamines)
aminoacids and pharmaceutical compounds in the presence of an organic superbase (eg DBU or
tetramethylguanidine) According with the optimized reaction conditions itacutes possible to tune the
chemical and thermal stability as well as potential application of the final salts
b) The potential use of scCO2 for extraction and separation processes in the case of three
asymmetric catalytic reactions in the presence of ionic liquids andor chiral ionic liquids as
solvent or chiral media respectively In particular Sharpless asymmetric dihydroxylation of olefins
(in the presence of osmium catalyst) asymmetric Aldol and Michael reactions (in the presence of
chiral organocatalysts based on chiral ILs) will be presented
The peculiar properties of carbon dioxide including as supercritical fluid open excellent
perspectives for the application in novel organic synthetic transformations as well as their use in
industrial processes
Acknowledgements We thank the Fundaccedilatildeo para a Ciecircncia e Tecnologia for financial support
(PEst-CEQBLA00062011 and PTDCCTM1036642008 projects and SFRHBD671742009 for
KZ PhD grant)
References 1 a) Goodrich B F de la Fuente J C Gurkan B E Zadigian D J Price E A Huang Y
Ind Eng Chem Res 2011 50 111 b) Camper D Bara J E Gin D L Noble R D Ind
Eng Chem Res 2008 47 8496
2 Afonso C A M Branco L C Candeias N R Gois P M P Lourenccedilo N M T Mateus
N M M Rosa J N Chem Commun 2007 2669
3 a) Carrera G V M da Ponte M N Branco L C Tetrahedron 2012 68 7408 b) Branco L
C Serbanovic A da Ponte M N Afonso C A M ACS Catalysis 2011 1 1408 c) Carrera
G V SM Costa A Ponte M N Branco LC Synlett 2013 24 2525
129
P18
1H AND
13C ASSIGNMENTS OF THREE SERIES BIOACTIVE
IMIDAZO[21-B]THIAZOLE DERIVATIVES
AS Bunev EV Sukhonosova GI Ostapenko PP Purygin
Togliatti State University Togliatti Russia
The complete 1H and
13C NMR assignments of three series bioactive imidazo[21-b]thiazoles were
achieved by combination of one and two-dimensional NMR experiments and the NMR signals of
these compounds were analyzed and compared
The authors are grateful to the Ministry of Education and Science of the Russian Federation (State
job No 426)
130
P19
SYNTHESIS OF 145-TRISUBSTITUTED IMIDAZOLES CONTAINING
TRIFLUOROMETHYL GROUP
AS Bunev MA Vasiliev GI Ostapenko VE Statsyuk
Togliatti State University Togliatti Russia
A new synthetic protocol for the synthesis of 145-trisubstituted imidazoles (2a-i) containing
trifluoromethyl group has been developed using van Leusen reaction which incorporates two-
component condensation reaction trifluoroacetimidoyl chlorides (1a-i) with tosylmethylisocyanide
This protocol provides a novel and improved method for obtaining trifluoromethyl containing 145-
trisubstituted imidazoles in good yields
The authors are grateful to the Ministry of Education and Science of the Russian Federation (State
job No 426)
131
P20
THE QUANTUM-CHEMICAL STUDY OF THE KEY STEP OF THE
CYCLIZATION OF 411-DIMETHOXY-510-DIOXO-2- ANTHRA[23-B]-
FURAN-3-CARBOXYLATES
EE Bykov AS Tikhomirov AE Shchekotikhin MN Preobrazhenskaya
Gause Institute of New Antibiotics RASM Moscow Russia
Highly active inhibitors of topoisomerase I capable of blocking the growth of tumor cells with
activated mechanisms of multiple drug resistance were discovered in the series of derivatives 411-
dihydroxy-510-dioxoanthra[23-b]furan-3-carboxylic acids [1] Previously a scheme of preparation
of 2-substituted derivatives of 411-dimethoxy-510-dioxoanthra[23-b]furan-3-carboxylic acids was
developed However yields of anthrafurandiones by this method seriously depended on a substituent
in position 2 [2] To understand this a quantum-chemical estimations of the key step of the
intermolecular cyclization of the intermediate enol forms of ethyl 2-(3-bromo-14-dimethoxy-910-
dioxo-910-dihydroanthracene-2-yl)-3-hydroxypropanoates 1a-c to the corresponding anthra[23-
b]furan-510-diones 2a-c were carried out
The quantum-chemical calculations by DFT method B3LYP6-31+G(d) by means program package
Gaussian-09 [3] confirmed that the activation barriers (ΔE
) of cyclization of enol form 1a-c
depend on the nature of the substituent R The groups R that have different electronic properties
influence actively on the electron density of the internal nucleophile what is enolic oxygen atom
(see Table QO and ΕHOMO) The calculated values of ΔE
correlate with the yield of the anthra[23-
b]furan-510-diones 2a-c [2] Thus quantum-chemical evaluation of the key step of cyclization
confirmed that the electron-withdrawing substituents reduce the reactivity of enol intermediates 1a-
c in the cyclization to the corresponding anthra[23-b]furan-510-diones 2a-c
Table Parameters for the reaction of cyclization of anthra[23-b]furan-510-diones 2a-c
Derivative 2a 2b 2c
R -CH3 -Ph -CF3
ΔE (kcalmol) 2184 227 2586
ΕHOMO (ev) -201 -223 -245
QO -0687 -0577 -0567
The yield [2] 72 40 3
References
1 Shchekotikhin A E et al Patent RU 2412166 (2011)
2 Tikhomirov A S Shchekotikhin A EChem Heterocycl Compd 2014 50 271
3 httpwwwgaussiancom
132
P21
MACROPOLYCYCLIC COMPOUNDS COMPRISING DIAZACROWN
ETHER MOIETIES AND FLUOROPHORE GROUPS
NM Chernichenko AD Averin IP Beletskaya
MV Lomonosov Moscow State University Department of Chemistry Moscow Russia
Macrobicyclic compounds comprising structural fragments of diazacrown ethers and oxadiamines
were synthesized using Pd-catalyzed amination reactions using Pd(dba)2BINAP system [1] They
were further modified with various fluorophore substituents using catalytic and non-catalytic
approaches to create promising fluorescent chemosensors and molecular probes for metal cations
Modification was carried out at N atoms of the cryptand and at C atoms of the benzyl spacer
Macrotricycles and isomeric trismacrocycles were obtained via Pd-catalyzed macrocyclization
reactions of NNrsquo-bis(35-dibromobenzyl) diazacrown ether derivatives with oxadiamines using
either BINAP or RuPhos ligands and were further modified with dansyl fluorophores
Acknowledgement The work was financially supported by the RFBR grant N 12-03-93107
[1] AA Yakushev NM Chernichenko MV Anokhin AD Averin AK Buryak F Denat IP
Beletskaya Molecules 2014 19 940-965
133
P22
SYNTHESIS OF 1Н-IMIDAZOLECARBOXAMIDES
IV Zavarzin VN Yarovenko SL Semenov EI Chernoburova MM Krayushkin
N D Zelinsky Institute of Organic Chemistry Laboratory for Chemistry of Steroid Compounds
Moscow Russia
We earlier proposed the method for synthesis of 45-dihydro-1Н-imidazolecarboxamides (1) by the
reaction of chloroacetamides with aliphatic diamines in the presence of sulfur12
(Scheme 1)
R N H
O
C lH
2N(C H
2) n
2N H
2
R N H
O
NH
( C H2)
N
1n n = 1 2
Scheme 1
In this work we propose the method for the transformation of products 1 into 1Н-
imidazolecarboxamides 2 We found that the interaction of 1а-с with NiAl alloy in aqueous
methanol at 20оС results in the dehydrogenation of dihydroimidazole fragments to form imidazoles
2а-с
NN
NH
O H
R
NN
NH
O H
R
Ni A l K O H
M e O H H2O
1 a -c 2 a -c
R = 2 -F 3 -O M e 2 4 -M e
Scheme 2
References
1 VN Yarovenko SA Kosarev IV Zavarzin MM Krayushkin Russ Chem Bull (Int Ed)
1999 No 4 p 753
2 MM Krayushkin VN Yarovenko IV Zavarzin Russ Chem Bull (Int Ed) 2004 No 3 p
491
134
P23
FEPMD PROTOCOL TO MODEL SELECTIVITY OF KINASE
INHIBITORS
GG Chilov OV Stroganov FN Novikov AA Zeifman VS Stroylov IYu Titov IV
Svitanko
ND Zelinsky Institute of Organic Chemistry RAS
With over 500 different kinase enzymes encoded in a human genome and appreciation the role of
kinases as promising therapeutic targets the selectivity profile of a kinase inhibitor is an important
indicator of its potential off-target effects including adverse effects which sometimes might be
quite severe and even preclude application of a drug in clinical practice One of the recent examples
of how the lack of selectivity of a kinase inhibitor drug may restrict its clinical application because
of abundant life-threatening adverse effects is presented by Ponatinib - a potent inhitor of Abl
kinase (primary therapeutic target) as well as over 40 off-target kinases With the intent to
overcome adverse effcts of Ponatinib we designed a PF-114 molecule which appeard to be
comparable to Ponatinib with respect to Abl suppression but inhibited only 10 off-target kinases In
order to rationalize enhanced selectivity we established a FEPMD protocol in which for each
kinase Ponatinib molecule was transformed to PF-114 and the dG of such transition was recorded
The modeled system consisted of a full atom kinase domain with inhibitor docked into ATP-bindin
site and immersed in a box of explicit solvent FEP transition was split into 3 steps decharging
initial molecule (Ponatinib) converting Van der Waals parameters to another molecule (PF-114)
and then charging the resulting molecule Each transition was split in its turn into 10 windows each
taking 2 ns of MD simulation Totally 15 kinases were modeled for the selectivity of inhibition It
appeared that calculated selecivities correlaeted with experimental data with R of 063 Structural
findings from FEPMD simulations uncovered 2 factors contributing to the enhanced selectivity of
PF-114 its unfavorable (compared to Ponatinib) interaction with main chain carbonyl oxygen
present in the active site of BRAF Src ERBB4 FGFR1 VEGFR2 TRKC TRKB and
unfavorable interaction with water molecule in the active sites of BRAF EPHA7 FGFR1 FLT1
MAPK11 MAPK14 kinases Current results suggests that full atomic FEPMD modeling may be a
valuable instrument in the design of kinase inhibitors with improved selectivity
135
P24
FEATURES OF NATURAL POLYSACCHARIDE BASED THIN FILMS
FORMATION
YV Chudinova2 DV Kurek
2
1 - MVLomonosov Moscow State University Moscow Russia
2 - Centre laquoBioengineeringraquo RAS Moscow Russia
Natural polysaccharide based thin films are promising biomaterials for using in different fields of
science Thin films were prepared by layer-by-layer (LbL) technique via alternately dipping the
substrate into polycation and polyanion solutions to form polyelectrolyte multilayers During each
adsorption cycle one a monolayer is built up and the surface charge is reversed This assembly
process allows obtaining films with desired characteristic Layer-by-layer method offers several
advantages over other thin film deposition techniques for example it is simple rapid and
inexpensive
Polyelectrolyte LbL films can be assembled from chitosan pectin and other natural polymers
Pectin is one of the basic components of plant cell wall It has a complex structure and contained
linear and branched regions Chitosan is produced by deacetylation of chitin which is the structural
element in the exoskeleton of crustaceans and cell walls of fungi Chitosan and pectin are
considered as some of the most attractive natural polyelectrolytes because they are nontoxic
biodegradable and biocompatible polymers Their oppositely charged surface permits to use them
for generating biocompatible surfaces via multilayer assembly
The main characteristic of biofilms such as surface topography roughness thickness molecular
structure adhesion forces were determined by atomic force microscopy (AFM)
Influence of polyelectrolyte type and number of layers on the film buildup were investigated Pectin
covers mica surfaces very well and filling degree is nearly 100 Chitosan forms heterogeneous
structures on the mica surface with a lesser filling degree Chitosan with different molecular weight
was studied Results showed that in all cases were formed particles and aggregates
Influence of substrate type and its possible modifications was considered Surface topography
height roughness of the films which formed on the substrates with different properties were varied
Further effect of the concentration and the presence of other polysaccharide were observed Pectin-
chitosan and chitosan-pectin coatings which formed via layer-by-layer technique had different
morphological characteristics
The adhesion of the polyelectrolyte multilayer films has been investigated by contact mode of
AFM Adhesion is the attraction forces between the AFM tip and the film surfaces by force-curves
mode [1] Obtained data demonstrated relationship between adhesion forces and surfaces properties
Understanding of the molecular structure and pathways of formation such thin films allows to
predict the characteristics and produce coating materials for use in various fields of biology and
medicine
References
1 Guo Y-B Wang D-G Adhesion and friction of nanoparticlespolyelectrolyte multilayer films
by AFM and micro-tribometer Tribology International- N 44 - P 906ndash915 - 2011
136
P25
SYNTHESIS OF N-(PICRYLAMINO)NITROPYRAZOLES
IL Dalinger IA Vatsadze TK Shkineva AV Kormanov SA Shevelev
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Laboratory of
Nitrogen-containing Aromatic Compounds Moscow Russian Federation
One of the directions of modern design of nitroazole-based high-energy compounds consists in the
introduction of an N-amino group to the endocyclic nitrogen atom of the nitroazole ring This
results in the preparation of N-amino derivatives of nitrotetrazole [1] nitrotriazoles [1-3]
nitroimidazoles [4] and nitropyrazoles [3 5-8]
However the possibility functionalization N-aminonitroazoles additional energy-rich groups with
saving of nitro groups in azole cycle poorly understood and limited only N-nitration [4a] N-
trinitroethylation [3 4c] and the introduction of a fragment of [124]triazolo[43-b]-
[1245]tetrazine [9]
In continuation of our works on chemistry of polynitropyrazoles [10] and for the purpose of
broadening of synthetic potential of N-aminonitroazoles as versatile building-blocks for
constructing new energy-rich compounds we developed method functionalization N-amino group
using picryl fragment on the example of N-aminonitropyrazoles 1
This method is based on arylation N-aminonitropyrazoles 1 under the action of picrylchlorid (PicCl)
in the presence of base (К2СО3) when heated in MeCN within 2-6 h The result is synthesized
representatives of a previously unknown type of energy-rich compounds - N-
(picrylamino)nitroazoles 2 which are isomers well known C-(picrylamino)nitroazoles [11]
Compounds 2 with two nitro groups in the pyrazole ring are organic NH-acids medium strength
(рКа 40 - 45 in MeCN-Н2О) [1] TM Klapoumltke DG Piercey J Strierstorfer Dalton Trans 2012 41 9451
[2] P Yin Y Zhang DA Parrish JM Shreeve J Mater Chem A 2013 1 585
[3] Y Zhang DA Parrish JM Shreeve J Mater Chem A 2014 2 3200
[4] (a) R Duddu PR Dave R Domavarapy N Gelber D Parrish Tetrahedron Letters 2010 51 399 (b)
MM Breiner DE Chavez DA Parrish Synlett 2013 24 519 (c) P Yin Y Zhang Y Zhang DA
Parrish JM Shreeve J Mater Chem A 2013 1 7500
[5] G Herveacute C Roussel H Graindorge Angew Chem Int Ed Engl 2010 49 3177
[6] C He J Zhang DA Parrish JM Shreeve J Mater Chem A 2013 1 2863
[7] VM Vinogradov IL Dalinger SA Shevelev Mendeleev Commun 1993 111
[8] X Zhao C Qi L Zhang Y Wang S Li F Zhao S Pang Molecules 2014 19 896
[7] NV Palysaeva KP Kumpan MI Struchkova IL Dalinger AV Kormanov NS Aleksandrova
VM Chernyshev DF Pyreu KYu Suponitsky AB Sheremetev Оrg Lett 2014 16 406
[10] (a) IL Dalinger IA Vatsadze TK Shkineva GP Popova SA Shevelev Synthesis 2012 44 2058
(b) IL Dalinger IA Vatsadze TK Shkineva GP Popova SA Shevelev YV Nelyubina J
Heterocycl Chem 2013 59 911
[11] (a) PN Neuman J Heterocycl Chem 1970 7 1159 (b) MD Coburn J Heterocycl Chem 1970 7
345 and 1971 8 153
The research was supported by the Division of Chem and Material Sciences of the RAS (OKh-4)
137
P26
MeLaOXZrO2 CATALYSTS FOR CO OXIDATION
NA Davshan AL Kustov OP Tkachenko LM Kustov
IOC RAS Lab14 Moscow Russia
Mixed metal oxides with a composition АВО3 known as perovskites exhibit the high thermal
stability and enhanced catalytic activity in CO and hydrocarbon oxidation The perovskite-type
materials are less expensive as compared to supported noble metals The materials can be
significantly improved by supporting the perovskites onto porous carriers with a developed surface
area The goal of our work was to prepare characterize and test in CO oxidation a series of MeLaO3
perovskites (Me = Co Fe Ni) supported onto a mesoporous zirconia as a robust and durable carrier
The synthesis of mesoporous ZrO2 was carried out according to the previously developed and
modified procedure [1] A glycine complex of lanthanum and cobalt or iron or nickel was prepared
by the recipe described in [2 3] The samples of supported lanthanum-metal perovskites were
prepared by impregnation of the precalcined mesoporous carrier (ZrO2) with a solution of the
prepared La-CoFeNi glycine complex
The chemical analysis of the samples for the contents of the metals (Zr Co Ni Fe and La) was
carried out by atomic emission spectroscopy
Diffuse-reflectance FTIR spectra were recorded at room temperature in the frequency range of
6000-400 cm-1
with a resolution of 4 cm-1
using а NICOLET ldquoProtegerdquo 460 spectrometer supplied
with a diffuse-reflectance attachment The following probe molecules were used to test surface sites
of different nature СО as a probe for Lewis acid sites and low-coordinated metal ions CD3CN as a
probe for both Lewis and Broensted (if present) acid sites The probe molecules were adsorbed at
room temperature and equilibrium pressures of 5 Torr for СО 96 Torr for CD3CN (saturated
pressures)
The phase composition of the samples and the particle size of the supported metal were examined
by X-ray diffraction (XRD) analysis X-ray absorption (XANES + EXAFS) spectra (Co K edge at
7709 eV and Ni K edge at 8333 eV) were measured at the Hasylab X1 station (DESYGermany)
using a Si(111) double crystal monochromator The EXAFS data analysis was performed using the
software VIPER [4] Reference spectra were taken using standard reference compounds CoO
Co3O4 Co-foil NiO and Ni -foil The required scattering amplitudes and phase shifts were
calculated by the ab initio FEFF810 code [6] X-ray photoelectron spectra were recorded by XSAM
800 spectrometer with Mg Kα X-ray (12536 eV) source
Catalyst testing was carried out in a laboratory scale fixed bed quartz reactor (internal diameter 3
mm) operating at an atmospheric pressure The feed gas mixture consisted of 45 vol CO 225
vol O2 and He balance The total feed flow rate was held constant at 10 cm3min with a volume
hourly space velocity (VHSV) of 6000 hminus1
The following order of the activity in CO oxidation as the temperature of the 50 conversion (T50)
was found in the temperature range from 50 to 400degC LaCoO3ZrO2 (200oC) gt LaFeO3ZrO2
(275oC) gt LaNiO3ZrO2(300
oC)
[1] V A Sadykov L A Isupova I A Zolotarskii L N Bobrova A S Noskov V N Parmon E
A Brushtein T V Telyatnikova V I Chernyshev V V Lunin Appl CatalA 204 (2000) 59
[2] EV Makshina Thesis of Cand Sci Dissertation Moscow State Univ 2008
[3] LM Kustov Top Catal 4 (1997) 131
[4] KV Klementiev wwwcellesBeamlinesCLAESSsoftwareviperhtml
[5] AL Ankudinov B Ravel JJ Rehr SD Conradson Phys Rev B 58 (1998) 7565
138
P27
SELECTIVE FUNCTIONALIZATION OF ALKYNES WITH NATURALLY
OCCURRING ORGANOSULFUR COMPOUNDS
ES Degtyareva VP Ananikov
Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
Nowadays crude oil remains one of the most important resources in the industry Crude oil is a
complex mixture mostly of hydrocarbons with small amounts of sulfur- and nitrogen-containing
impurities To produce more valuable fuels oil fractions are subject to catalytic processes like
reforming isomerization and cracking For ecological as well as technological reasons
organosulfur components should be removed before the petroleum refining However it would be
much more interesting to utilize these sulfur species as a naturally-occurring source of chemical
reagents for example for functionalization of hydrocarbons
The promising and efficient way to create a C-S bond is an addition reaction of thiols and disulfides
to unsaturated hydrocarbons [12] A convenient and selective metal-catalyzed methods for the
addition of thiols and disulfides to alkynes have been recently reported The present study is
dedicated to the development of such catalytic system in order to involve crude oil as a reagent in
organic synthesis
As the first step in our study we describe analytic approach for high sensitivity mass spectrometric
measurements with ability to detect trace amount of products Since most of the components in the
crude oil are nonpolar special polar tags were introduced for electrospray ionization (ESI)
detection To achieve this aim the alkynes with easily polarizable groups were synthesized Good
results were achieved using 1-(pentyn-4)-1H-imidazole and in the model reaction involving the
mixture of C6H5SH C6H11SH and C6H13SH all products were clearly detected (Figure 1) Detailed
study of the catalytic system and ESI-MS characterization will be presented and discussed
Figure 1 An example of ESI spectrum registered for the reaction mixture in the crude oil
(1) Ananikov V P Kabeshov M A Beletskaya I P Khrustalev V N Antipin M Y Organometallics
2005 24 1275ndash1283
(2) Ananikov V P Orlov N V Zalesskiy S S Beletskaya I P Khrustalev V N Morokuma K
Musaev D G J Am Chem Soc 2012 134 6637ndash6649
139
P28
PLATINUM GROUP METALS COMPLEXES OF HYBRID CHALCOGEN
LIGANDS SYNTHESES STRUCTURES AND CATALYSTS IN C-C
COUPLING REACTIONS
S Dey
Chemistry Division Bhabha Atomic Research Centre Mumbai- 400 085 India
The chemistry of chalcogenated platinum group metal complexes has been of considerable interest
for several years due to their fascinating structural features their relevance in catalysis [1] and
lately in materials science [23] These complexes are mostly non-volatile insoluble or poorly
soluble oligomeric species in organic solvents thus limiting their utility as precursors for the
synthesis of metal chacogenides for electronic devices or making them inconvenient for any
homogeneous catalysis reaction To inhibit polymerization of metal chalcogenolates and to develop
phosphine free Pd-catalysts internally functionalized ligands containing both soft chalcogen and
hard N donor atoms has been quite successful such as pyridine chalcogenolates [4] or aliphatic
amine chalcogenolate ligands [56]
We have designed and developed several internally functionalized ligands (N E)2 N EAr (E = S
Se Te N E = Me2NCH2CH2E Me2NCH2CH2CH2E Ar = Ph tol Mes) and bis(4-
pyridyl)dichalcogenide and synthesized their palladium(II) and platinum(II) complexes Versatile
coordination behaviour of these ligands are shown in their complexes (Chart 1) The unusual colour
of [MCl(E N)(PR3)] (blue-violet Pd red Pt) has been attributed due to metal mediated ligand (E)
ndash to ndash ligand (PR3) charge transfer transitions The cationic complexes [Pt(PEt3)2(py2E2)]2(CF3SO3)4
with Pt pyridyl bond have been isolated via self-assembly reaction The complexes
[PdCl2(N EAr)]n exist in monomer and dimer forms their ratio depends on the size of chelate ring
and chalcogen atom The catalytic activity of [PdX(N E)]n (X = Cl OAc) [PdCl2(N EAr)]n and
trans-[PdCl(4-Sepy)(PPh3)2] in Suzuki C C cross coupling reaction will also be discussed
Chart
M
E
E
M
N
N
M
E
E
M
X
NX
N
M
E
N
M
E
N
M
N
E
X
X
X
X
Ar
Ar E
N
M
N
E E
N
M
N
E E
N
M
M
E
N
M
EN
+4
Acknowledgement Dilip Paluru K V Vivekananda A Wadawale N Bhuvanesh B M Bhanage and V K Jain are
acknowledged for collaborations
References
1 Q Yao E P Kinney C Zheng Org Lett 2004 6 2997 2999
2 S Dey V K Jain Platinum Met Rev 2004 48 16 29
3 B Radha G U Kulkarni Adv Funct Mater 2010 20 879 884
4 K V Vivekananda S Dey A Wadawale N Bhuvanesh V K Jain Dalton Trans 2013 42
14158 14167
5 D K Paluru S Dey A Wadawale V K Jain J Organomet Chem 2013 728 52 56
6 B J Khairnar S Dey V K Jain B M Bhanage Tetrahedron Lett 2014 55 716 719
140
P29
THE REACTIONS OF 13-DIARYL-3-CYCLOHEXANONILPROPANE-1-
ONE WITH HYDROGEN SELENIDE IN SITU IN CONDITIONS OF ACID
CATALYSIS
DYu Direnko1 YaB Drevko
2 BI Drevko
2
1 - Penza branch of the military Academy of logistics
2 - FGU VPO Saratov State Agrarian University named after NI Vavilov
It is known that when arylaliphatic 15-dicetones interacts with hydrogen selenide in conditions of
acid catalysis the corresponding 4H-selenopyran structures can be formed 1 which are used as
veterinary and healthcare products However dicyclic diaryl-4H-selenopyrans have not been
described until today
We have studied the chemical reaction of 1-paramethoxy-3-phenyl-3-cyclohexanonilpropane-1-one
1 with hydrogen selenide in situ in conditions of acid catalysis The reaction has been conducted in
the presence trimethoxyphosphine 1 In the result of the compound 1 was obtained in 2-
paramethoxy-4-phenyl-5678-tetrahydro-4H-selenochromen 2 with quantitative output ndash 80
(Melting point = 108-1090С)
O O S e
C H3
O H P C l3 Z n S e
p
1 2
P h
P h
P h
P h - O C H3
p - O C H3
In the course of reaction settled crystal compounds and mother solution were analyzed by method
of the capillary gas-liquid partition chromatography with mass-selective detector HP 58905972
Tinj=200оС tset=3 min Tset=50
оС Tend=280
оС Т = 10
оСmin carrier gas ndash helium
= 1 mlmin
It was found that every molecular ion or fragment which contained selenium presented in the form
of six signal intensities conforming to the content of the selenium isotopes in the nature Se74
(087) Se76
(902) Se77
(758) Se78
(2352) Se80
(4982) Se82
(919)
The compound 2 is subjected to isomerisation at high temperature So there are signals of four
compounds with retention time 2703 min 2906 min 293 min 4008 min on the chromatogram
(mz = 381 the output of this molecular ion is accompanied by loss of one hydrogenrsquos isotope)
As well as one compound was identified and its molecular ion was conformed to
dehydroselenochromen (mz = 380 retention time is 3335 min) This ion also was identified
through GH-MS that confirmed the received mass spectrum
Therefore formation of product (dehydroselenochromen (mz = 380)) demonstrates the new
direction of disproportionation of dehydroselenochromen structures on alicyclic fragment
Literature
1 Drevko YaB Fedotova OV The synthesis of the first representatives of benzenediamine
dehydroselenochromens CHC200610P1586-1587
141
P30
SYNTHESIS OF UNNATURAL PROLINE DERIVATIVES USING THE AZA-
COPE-MANNICH-REACTION
DS Belov NK Ratmanova AV Kurkin IA Andreev
Lomonosov Moscow State University
Oxygenated bicyclic amino acids constitute an important class of secondary metabolites Many of
these nonproteinogenic amino acids are subunits of structurally diverse natural products Various
methods to access these biologically important compounds were advised by synthetic community
and subsequently used by pharmaceutical companies However pharmaceutical industry usually
relies on the most robust and reliable reactions
Aza-Cope-Mannich rearrangement is a powerful reaction which was successfully used in academia
settings was however largely overlooked by medicinal chemists1 We have shown recently that it
can be routinely scaled up to 1 mole23
In this work we demonstrated that a number of proline
analogs can be efficiently prepared with full control of stereochemistry
Scheme 1
The aminoalcohols required for the rearrangement were effectively prepared in several steps form
commercially available oxiranes (Scheme 1) The aza-Cope-Mannich reaction provided both cis and
trans fused unnatural proline analogs 2 3 or 4 in high yields The ratio of products was dependent
upon the reaction conditions and the nature of substituents R1 and R2 The reaction also proved to
be scalable (gt1 g)
This study was supported by the Russian Foundation for Basic Research (Projects No 14-03-
31685 14-03- 31709 14-03-01114)
1 Overman L E Humphreys P G Welmaker G S Org React 2011 75 747-820
2 Belov D S Lukyanenko E R Kurkin A V Yurovskaya M A Tetrahedron 2011 67
9214ndash9218
3 Belov D S Lukyanenko E R Kurkin A V Yurovskaya M A J Org Chem 2012 77
10125ndash10134
142
P31
SYNTHESIS OF OXYGENATES OF DIFFERENT CLASSES ON
HETEROGENIOUS KCOMOS-CATALYSTS
VS Dorokhov OL Eliseev AL Lapidus VM Kogan
N D Zelinsky institute of organic chemistry Moscow Russia
Heterogeneous catalytic systems based on alkali-modified molybdenum disulphide are promising
for alcohols synthesis from СО and Н2 [12] The model of dynamic nature of the active sites of
transition metal sulphide catalysts was taken as a conceptual basis for the work [3]
We conducted investigations of structure and functioning mechanism of MoS2-based catalysts
active phase in oxygenates synthesis reaction We found out that alkali metal (potassium) forms
unite phase with MoS2 and significantly changes it structure Addition of potassium increases
average number of layers and average linear size of MoS2 crystallites As it follows from our
catalytic experiments both Co and K increases selectivity of alcohols formation Besides addition
of potassium suppresses hydrogenation and hydrodesulphurisation reactions [4]
We suggested that formation of alcohols from СО and Н2 occurs on active sites located on the
edges of the MoS2 slabs It is likely that active sites responsible for alcohols synthesis consist of a
combination of two MoS2 clusters one of which is promoted with Co and K is intercalated
between the crystallite layers Formation of alcohol molecule depends on accessibility of alkali ion
to coordination of alcoxyl intermediate oxygen The scheme of possible mechanism of synthesis-
gas conversion on KCoMoS catalyst was published in [5]
The addition of ethanol or ethylene to synthesis gas substantially changes the reaction rate and
composition of the products [5] Presence of these components in the gas feed can significantly
increase CO conversion According to our results alcohols can adsorb on KCoMoS-catalysts active
sites and enter a series of side reactions which leads to formation of ethers esters aldehydes
ketones and organic acids Therefore the use of additives to syngas makes it possible to obtain a
wide range of oxygenates of different classes The further development of this approach can be
efficient for controlling selectivity in processes of simultaneous synthesis of various classes of
organic compounds
Acknowledgment This work was financially supported by the Russian Foundation for Basic
Research (Project No 14-03-31769 mol_a)
References
1) Surisetty VR et al App Cat A 404 (2011) 1-11
2) Feng M Recent Patents Catal 1 (2012) 13-26
3) Kogan VM Nikulshin PA Rozhdestvenskaya NN Fuel 100 (2012) 2ndash16
4) Dorokhov VS et al Kinetics and Catalysis 54 N 2 (2013) 243ndash252
5) Kogan VM et al Russ Chem Bull 2 (2014) in press
143
P32
THE MECHANISM OF ALCOHOL FORMATION OVER TMS CATALYSTS
VS Dorokhov1 EA Permyakov
1 OL Eliseev
2 VM Kogan
1
1 - ND Zelinsky Institute of Organic Chemistry RAS Laboratory of catalysis by trasition metals
and their compounds Moscow Russia
2 - ND Zelinsky Institute of Organic Chemistry RAS Laboratory of catalytic reaction of carbon
oxides Moscow Russia
The aim of this work is to investigate a structure of transitional metal sulfide (TMS) catalyst active
sites in mixed alcohol synthesis (MAS) from synthesis gas and to develop possible mechanism of
this reaction The model of dynamic nature of the active sites of TMS catalysts was taken as a
conceptual basis for the work [12] As it follows from our catalytic experiments both Co and K
affect alcohol selectivity towards hydrocarbon (HC) formation It is likely that the active sites
responsible for alcohol formation are located on the edges of the MoS2 slabs Besides K poisons
C-S hydrogenolysis sites and HDS activity decreases Basing on the experimental data we suggest
the structure of the MAS site as a combination of two MoS2 clusters one of which is promoted with
Co and K is intercalated between the crystallite layers and the scheme of possible mechanism of
synthesis-gas conversion on K-Co-Mo-S catalysts (Fig 1)
C O
nC O
CH3OH
C n+1 H 2n+3 OH
2 H
H
H
H
H
K
C
S
C o
M o
S
S
S
S
S
M o
M o
H
C H 4
3 H
H2O
M o
K
H
H
CO
S
C o
M o
S
S
S
S
S
M o
M o
K
C O
S
C o
M o
S
S
S
S
S
M o
M o
K
C H3
S
C o
M o
S
S
S
S
S
M o
M o
H
K
C H3
S
C o
M o
S
S
S
S
S
M oO
M o
H
HH
K
CO
S
C o
M o
S
S
S
S
S
M o
M o
K
C H2
S
C o
M o
S
S
S
S
S
M o
O
H
M o
K
S S
C o
M o
S
SS
S
M o
H H
K
C O
CnH
2n+1
S
C o
M o
S
S
S
S
S
M o
M o
2 H
effec t
of K
C
o
and s
upport
(4 n -4 )H(n -1 )H
2O
CnH
2n+1 M o
H
K
C H2
S
C o
M o
S
S
S
S
S
M o
CnH
2n+1 M o
K
CH2
S
C o
M o
S
S HO
S
S
S
M o
Cn+1
H2n+4
H2O
3 H
H
CH3
M o
K
C O
Cn-1
H2n-2
S
C o
M o
S
S
S
S
S
M o
eff
ec
t o
f K
C
o a
nd
su
pp
ort
Fig 1 Suggested
mechanism of
alcohols and HC
formation over
KCoMoS active
sites Black
rectangle defines
the initial step of
reaction As an initial step of the mechanism CO adsorption on the vacancy was taken After partial
hydrogenation of carbon by dissociatively adsorbed hydrogen the C=O bond lengthens allowing
the oxygen atom to coordinate on K+ ion intercalated between the MoS2 crystallite layers
Coordination of the oxygen on the K+ ion stabilizes the alkoxylenated intermediate and prevents the
C-O bond from breaking which is necessary for the succeeding process of alcohol formation
Oxygen coordination onto the Mo atom of the neighboring cluster leads to hydrogenolysis of the C-
O bond The alkyl fragment can either be hydrogenated to form HC or take part in the carbon-chain
growth ndash next CO molecule is inserted between C and Mo Oxygen of a newly inserted CO can
coordinate on K or Mo determining formation of either alcohols or HC It was found that the ratio
of alcohols to HC yields decreases with an increase of reaction temperature It means that alcohols
formation becomes kinetically less favorable at higher temperatures than the C-O bond
hydrogenolysis This observation is in agreement with the suggested mechanism
[1] VM Kogan PA Nikulshin NN Rozhdestvenskaya Fuel 100 (2012) 2ndash16
[2] VM Kogan PA Nikulshin Catal Today 149 (2010) 224ndash231
144
P33
CATALYTIC CYCLOMAGNESIATION OF 12-DIENES IN THE
SYNTHESIS OF PHEROMONES AND ACETOGENINErsquoS PRECURSORS
VA Dyakonov AA Makarov OA Trapeznikova UM Dzhemilev
Institute of Petrochemistry and Catalysis Russian Academy of Sciences Laboratory Catalytic
Synthesys Ufa Russia
An efficient method for the synthesis of valuable N- О- and Si-containing 1Z5Z-diene compounds
was developed The method comprises Cp2TiCl2-catalyzed cross-cyclomagnesiation of 12-dienes
by Grignard reagents (RMgRrsquo) to give 25-dialkylidenemagnesacyclopentanes in up to 96 yields
This approach was successfully used in the synthesis of 5Z9Z-dienoic acids precursors of
acetogenins and insect pheromones
Q
R
RQ
M g
RQE tM g B r
[T i] M g()n
+1
[T i] = C p2T iC l
2 n = 1 Q = T M S R = B n (k ) H ex ( l) n = 2 Q = O B n R = H ex ( a ) Q = O T H P R = H ex (b ) Q =
O T H P R = B n (c ) Q = M o rp h R = B n ( h ) Q = M o rp h R = H ex ( i) n = 3 Q = T H P R = C1 2
H2 5
(d ) n = 4 Q = T H P
R = B u (e ) Q = T H P R = H ex ( f) n = 6 Q = T H P R = B u ( g )
2
H3O + (D
3O + )
3 4
( )n
( )n
Acylation of diene 4g with acetyl bromide gave hexadeca-7Z11Z-dien-1-yl acetate 5 the pink
bollworm Pectinophora gossypiella attractant in a final yield of 89
T H P O -( C H
2)
6T H P O -( C H
2)
6
M g
( C H2)
3M e
T H P O -( C H2)
6
( C H2)
3M e
( C H
2)
3M e
A c O -( C H2)
6
( C H2)
3M e
M e
O
B r
E tM g B r
[T i] M g H3O +
+
8 9
9 4
4g 5
3g
The same approach was used to obtain the key synthons in the preparation of some acetogenins
exhibiting high antitumor antimalarial and immunosuppressive activities Cross cyclomagnesiation
of 12-hexadecane and 2-(45-hexadiene-1-yloxy)tetrahydropyran followed by hydrolysis furnished
2-(hexacosa-4Z8Z-dien-1-yloxy)tetrahydropyran 4h (yield 84) which is the key intermediate in
the preparation of the acetogenin cis-Solamin 6
T H P OM g
O T H P
H2 3
C1 2
OH H
O HOH
O
O
O T H P
( )1 0
( )
2
E tM g B r [T i]
( )1 0
( )2
2 0 oC E t2O
H3O +
( )1 0
( )2 ( )
1 1
8 7
3h
4h 6
+
This work was performed under financial support from the Russian Science Fondation (Grant 14-
13-00263) and by Russian Foundation for Basic Research (Grant 14-03-97024)
145
P34
SYNTHESIS AND ANTIHELMINTIC ACTIVITY OF 5-O-DERIVATIVES OF
IVERMECTIN
IV Zavarzin1 MKh Dzhafarov
2 NV Krukovskaya
1
1 - ND Zelinsky Institute of Organic Chemistry RAS Moscow Russia
2 - KI Skryabin Moscow State Academy of Veterinary Medicine and Biotechnology Moscow
Russia
Ivermectin 1 and its derivatives are widely used as antihelmintic medical formulations In this case
the parasites eventually develop resistance to these substances12
It is therefore highly relevant to
develop new antihelmintic agents We were the first who obtained the 5-O-ivermectin derivatives 2
by acylation of an ivermectin 1 anhydrides of carboxylic acids In addition to the carboxylic acids
the corresponding esters and amides are also obtained
R 1 O
O
O O O
C H3
CH3
OH
O
CH3
O
O
O
C H3
C H3
O
RC H
3
C H3
O HO M e
M e O
O H
OO
R 1 =
2 R = M e E t
1 R = M e E t R 1 = H
Carboxylic acid 2 as well as their esters and amides show high antihelmintic activity
Literature
1 Tyrell К Leo F Veterinary Parasitology - 2009 - 11 - Р 98-102
2 Varady M Cobra J Letkova V Kovac G Veterinary Parasitology - 2009 - 2-3 ndash Р 267-
271
146
P35
TRENDS IN EVOLUTION OF ANTIPARASITIC CHEMICAL AGENTS
MKh Dzhafarov
KI Skryabin Moscow State Academy of Veterinary Medicine and biotechnology
Chemotherapy and prevention are of high priority in control of helminthoses and other dangerous
parasitoses of humans animals and plants [1]
However the intensive administration of antiparasitic preparations leads to development of
resistance which is one of the ways of biochemical adaptation of helminths insects and arthopods
to the first- and second-order environmental changes (the host and ecological niche occupied by the
host where certain stages of the complex-cycle pest metamorphoses take place) which necessitates
regular renewal of the range of chemical agents among different measures [2]
Systematization of the data on the antiparasitic substances in the light of new discoveries and
developments is an important step for a successful struggle against parasitic diseases
In particular based on the systemic analysis of features of the chemical structure of anthelminthic
substances the hypothesis on the viability of the targeted search for such compounds among the
derivatives of conditionally progenitor cyclic hydrocarbons ndash benzene indene naphthalene 1Н-
cyclopenth [a]-naphthalene anthracene and phenanthrene ndash by alternating absolutely unsaturated
and saturated structures including heterocyclic analogues containing nitrogen oxygen and sulfur
and different substitutes and functional groups was voiced
References
1 Dzhafarov MKh Russian J Agrobiology Animal biology series 2013 4 p26-44
2 Dzhafarov MKh Vasilevich FI Advances in Pharmacology and Pharmacy 2014 2 30-45
147
P36
RHODIUM-CATALYZED REDUCTIVE CARBONYLATION OF
IODOBENZENE
OL Eliseev TN Bondarenko TN Myshenkova AL Lapidus
NDZelinsky Institute of organic chamistry Moscow Russia
Aromatic aldehydes is useful class of products because of diverse reactivity of formyl group
Usually they are synthesized by GattermannndashKoch ReimerndashTiemann VielsmeierndashHaag and Duff
reactions However these methods suffers from drawbacks like low yield poor selectivity and
generating waste and side products12
Alternatively catalytic formylation (reductive carbonylation)
of aryl halides with synthesis gas in the presence of palladium phosphine complexes was firhst
reported in 1974 by Schoenberg and Heck3 and lately by Beller
4ndash6 and Nagarkar
7 groups
Somewhat surprisingly up to now rhodium was unexplored as a catalyst for reductive
carbonylation of aryl halides This encouraged us to test rhodium salts and complexes in reductive
carbonylation of iodobenzene as a model substrate I
+ C O + H 2
R h -ca tC H O
b ase
+ b aseH I
Rhodium phosphine complexes such as HRh(CO)(PPh3)3 and RhCl(CO)(PPh3)2 were found to be
excellent catalysts They surpass PdCl2(PPh3)2 in respect to activity and selectivity to benzaldehyde
Aromatic solvents such as toluene and o-xylene seems to be the most suitable medium Other
solvents such as heptane 14-dioxane MEK DMF and acetonitrile gave poor yield of
benzaldehyde In methanol solution methyl benzoate was the main product
Reaction is highly sensitive to the nature of the base Replacing NEt3 with NBu3 resulted in almost
threefold reduction in benzaldehyde yield Somewhat higher but still low yield was achieved with
Huumlnigs base Inorganic bases such as potassium and cesium carbonates gave poor iodobenzene
conversion and benzaldehyde yield
Synthesis gas pressure renders effect on reaction Iodobenzene conversion reaches 100 at a total
pressure of about 1ndash15 MPa and slightly decreases at higher pressure Both selectivity and yield of
benzaldehyde increase with pressure increasing while selectivity to benzene decreased Biphenyl is
a main product at atmospheric pressure but it fully disappears at a pressure 1 MPa and higher
In conclusion rhodium (I) triphenylphosphine complexes are good catalysts for reductive
carbonylation of iodobenzene The best catalyst formulation found 05 RhCl(CO)(PPh3)2 150
NEt3 toluene At 110degC and 15 MPa (COH2 = 11) iodobenzene is totally converted within 2
hours giving benzaldehyde with the yield of 88
References
1 F Aldabbagh Compr Org Funct Group Transform II 2005 3 99
2 L P Crawford S K Richardson Gen Synth Methods 1994 16 37
3 A Schoenberg R F Heck J Am Chem Soc 1974 96 7761
4 S Klaus H Neumann A Zapf D Sturbing S Hubner J Almena T Riermeier P Groszlig M
Sarich W-R Krahnert K Rossen M Beller Angew Chem Int Ed 2006 45 154
5 A Brennfuhrer H Neumann St Klaus T Riermeier J Almenab M Beller Tetrahedron 2007
63 6252
6 H Neumann R Kadyrov Xiao-Feng Wu M Beller Chem Asian J 2012 7 2213
7 A S Singh B M Bhanage J M Nagarkar Tetrahedron Letters 2011 52 2383
148
P37
MODELING OF THE ELECTROCHEMICAL IMPEDANCE IN ANODIC
DISSOLUTION OF IRON USING A GENETIC ALGORITHM APPROACH
AR Enikeev1 IM Gubaidullin
2 MA Maleeva
3
1 - Institute of petrochemistry and catalysis Laboratory of mathematical chemistry Ufa Russia
2 - Institute of petrochemistry and catalysis Laboratory of mathematical chemistry
3 - AN Frumkin Institute of Physical Chemistry and Electrochemistry RAS Moscow Russia
In order to predict the general corrosion damage to metals and alloys development of deterministic
models and the acquisition of values for various model parameters are of paramount importance
Now it is generally accepted that elucidating an intricate reaction mechanism by means of steady-
state techniques alone is a very difficult task [1] In fact the steady-state approach provides too little
information in comparison with the complexity of the process under investigation In the present
work we used model with three adsorbed species it was possible to explain the iron dissolution in
sulphate and chloride media
It was recently found that impedance diagrams reveal at least three time constants concerning the
faradaic process in the iron-sulphate systems was proposed by Keddam [2]
Reaction mechanis
The reaction kinetic parameters was calculated by genetic algorithm The experimental impedance
diagrams showed one high-frequency capacitive arc and three time constant at lower frequencies
appearing as inductive or capacitive loops They are attributed in the models respectively to the
double layer capacitance in parallel with the transfer resistance and to the relaxation of three
reaction intermediates
1 E J Kelly J Electrochem Sot 112 124
2 M Keddam R Mattos and H Takenoutl J Electro-them Sot 128 257 266 (1981)
149
P38
KINETICS AND MECHANISM OF THE CATALYTIC OXIDATION OF 4-
TERT-BUTYLPHENOL BY AQUEOUS SOLUTIONS OF H2O2 IN THE
PRESENCE OF TITANOSILICATES
LV Enikeeva IM Gubaydullin NF Murzasheva
Institute of petrochemistry and catalysis RAS Laboratory of mathematical chemistry Ufa Russia
Selective oxidation of phenol is of great interest in terms of education practically valuable product -
hydroquinone and catechol This work is part of studies on the oxidation of phenols in aqueous
solutions of hydrogen peroxide in the presence of metallosilicates
For initial evaluation of the activity of titanosilicate catalysts in oxidation reactions of organic
compounds we used a decomposition reaction of H2O2 in the absence of substrate We studied the
catalytic activity in the decomposition reaction metallosilicates H2O2 apparent activation energy of
the reaction in the presence of different samples metallosilicates were calculated expression for the
reaction rate which shows good agreement with the experimental data was proposed model
validation on the value is performed
A series of catalytic activity of the samples in the reaction of hydrogen peroxide decomposition was
created
At the moment we study the oxidation reaction of tretbutilfenola by aqueous solutions of H2O2 The
scheme of the reaction the reaction kinetic parameters was calculated
150
P39
NEW CHEMICAL TRANSFORMATIONS OF Ni(acac)2 WITH POSSIBLE
INVOLVEMENT OF SUPERATOMIC Ni2O2 CORE AS REVEALED BY ESI-
MS AND MSMS
DB Eremin VP Ananikov
Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
More than twenty signals of nickel-containing ions were detected upon studying of electrospray
ionization mass spectrum of the Ni(acac)2 sample prepared in a plastic tube However changing
sample preparation procedure to a glass vial gave a clear spectrum with four signals corresponding
to mz 2570141 [Ni(acac)2 + Na]+ mz 4130040 [Ni2(acac)3]
+ mz 53503838 [Ni2(acac)4 +
Na]+ and mz 6690285 [Ni3(acac)5]
+ (Figure 1A) A prominent difference in the spectra was
caused by various plastic-derived contaminants that were coordinated to the metal center
Figure 1 (A) ESI-MS spectra of solution of Ni(acac)2 in acetonitrile prepared under standard
conditions (with contaminant signals marked by blue symbols) and prepared without a contact with
plastic (mz = 250 ndash 1000 range acac = C5H7O2) (B) Experimental survival yield curves of most
abundant ions
CID (Collision-induced dissociation) MSMS experiments were carried out to estimate relative
stability and to study reactivity during fragmentation process Fragmentation of the bimetallic ion
[Ni2(acac)3]+
was of most interest Eight fragment ions of different composition were detected
Seven of them were formed as a result of CndashC CndashH and CndashO bond cleavage nevertheless they
retained the Ni2O2 core a supposed superatomic structure which caused exceptional behavior
observed in the fragmentation After the fragmentation at the applied collision energy of 40 eV
ketene pentyn-3-on-2 buten-3-on-2 acetaldehyde carbon monoxide and hydroxide-anion were
formed Other bi- tri- and monometallic species detected did not undergo such transformations
under MSMS conditions Survival yields were calculated (Figure 1B) and a series of relative
stability was proposed Ni2 gtgt Ni1 asymp Ni3 The signal of [Ni2(acac)3]+ remained as most intensive
after heating of the solution
Mass spectra with the similar ionic composition were obtained for vanadyl and copper(II)
acetylacetonates as well as after the addition of two-fold excess of acetylacetone to the solution of
the acetates M(OAc)2 (M = Ni Cu Pd) Chemical reactivity of detected ions and the role of
bimetallic species are currently under investigation
151
P40
FORMATION OF A COMPLEX WITH FLUOROGENE LABEL IS A
RELIABLE WAY OF CREATION OF AN EXPRESS-METHOD OF
ACETYLCHOLINESTERASE ACTIVITY ASSAY
OV Fateenkova ET Gainulina DK Gulikova SB Ryzhikov VN Fateenkov
IM Sechenov First Moscow State Medical University Faculty of
Pharmacy Russia Moscow
Assay of erythrocyte acetylcholinesterase (AChE) activity of human is widely used for the
successful decision of many problems facing to a modern science development of effective antidots
for treatment of defeats by toxic organophosphorus inhibitors medicines for treatment of illness
Alzheimer and Parkinson etc
In a lot of cases there is a necessity of express-analyses of defeat by toxic organophosphorus
inhibitors As an example it is possible to refer to events in the Tokyo underground in 1985 year
and also in territory of several syrian cities in 2013 year when in the terrorist purposes sarin has
been applied and there was a necessity of urgent diagnostics of a degree of defeat of significant
number of victims of this act of terrorism
Known methods of AChE activity assay do not correspond to modern requirements to correlation
of parameters ldquosensibility - time of formation of an analytical signalraquo
In the given work the express-method of acetylcholinesterase activity assay is offered on the basis
of formation of an intensively fluorescing complex by the given enzyme with fluorogene label
thioflavine T (TF) TF is reversible inhibitor of AChE and selectively binds to the peripheral site of
this enzyme
Figure Dependence of fluorescence intensity of TF (15 М) from AChE activity
With increase of AChE activity at constant concentration of ТF (15 М) in the investigated interval
of reagents concentrations the dependence of fluorescence intensity of system TF - AChE has
linear character (fig) At addition AChE to solution TF formation of an analytical signal (increase
of fluorescence intensity) on a wave of 490 nm is observed within of several seconds and the
achieved of fluorescence intensity remains stable more than 15 min The absence of influence of
human butirylcholinesterase and bull whey albumin on fluorescence intensity of thioflavine T on
length of a wave of 490 nm is confirms selective character of interaction of human erythrocyte
acetylcholinesterase with TF 1 De Ferrari GV Mallender WD Inestrosa NC Rosenberry TL J Biol Chem 2001 276 23282
2 Antokhin AM Gainullina ET Taranchenko VF Ryzhikov SB Yavaeva DK Russ Chem Rev 2010 79 8
713
152
P41
QUANTUM CHEMICAL MODELING OF CONFORMATIONS OF TERT-
BUTYL HYDROPEROXIDE
GT Garaeva VI Anisimova IA Suvorova NN Batyrshin
Kazan National Research Technological University 420015 Kazan KMarks 68
Data on internal rotation of tert-butyl hydroperoxide (TBHP) advance the field of conformational
analysis and can be used for investigation of reactivity of industrially important hydroperoxides
which are primary products of hydrocarbon oxidation processes
For TBHP internal rotation only about C-O and O-O bonds is possible Earlier it was demosntrated
that TBHP has two conformations ndash gauche and trans [1] Figure 1 (curves 12) shows that all
possible equilibrium structures of TBHP have identical energy while analysis of bond lengths and
angles (Table 1) also supports identity of these structures and therefore monomeric form of TBHP
exsists only in one conformation (Fig 2) [2]
Table 1 ndash Parameters of TBHP according to B3LYP6-311++G(dfp) calculations
Bond length Aring Angle deg Torsion angledeg OH
sm-1
С-О О-О О-Н СОО ООН С2С
1О
1О
2 С
3С
1О
1О
2 С
4С
1О
1О
2 С
1ООН
1450 1456 0966 1095 1002 -601 -1780 638 -1226 3785
1 Suvorov I A Association and the thermal decomposition of tertiary hydroperoxides Thesis
Candidate chem sciIA Suvorov - Kazan 2003 - 124 p
2 Anisimov VI Quantum-chemical study of the hydrogen bonds between molecules tertiary butyl
hydroperoxide VI Anisimova IA Suvorov NN Batirshin VI Sokolov KE Kharlampidi
Vestnik Bashkir University - 2008 - v 13 -3 (1) - p 793-797
The work was supported by Russian Ministry of Education and Science within the framework of
basic part (PNIL 0214)
Fig 1 ndash PES of internal rotation of BHP
1- around О-О bond 2 ndash around С-О bond
Fig 2 ndash Molecule of TBHP
153
P42
SUPRAMOLECULAR INTERACTION OF CAFFEINE MOLECULES WITH
EACH OTHER WATER MOLECULES AND OXYGEN ATOMS OF
TETRAOXIDOANIONS IN THE NEW COMPOUND COBALT
HEXAHYDRATE DIPERRHENATE CAFFEINE
KE German1 MS Grigoriev
1 GV Kolesnikov
2 YuA Ustynyuk
2 OI Slyusar
3 YaA
Obruchnikova3 OS Kryzhovets
3 MN Glazkova
3
1 - AN Frumkin Institute of Physical Chemistry and Electrochemistry RAS Moscow Russia
Medical Institute REAVIZ Moscow Russia
2 - Lomonosov Moscow State University Moscow Russia
3 - Medical Institute REAVIZ Moscow Russia
Recently the antitumor and radiosensitizing drugs being caffeine derivatives that penetrate easily
through blood brain barrier have been developed They are effective with radiation and
chemotherapy treatment for cases of brain tumors Results of these studies has shown the caffeine
derivatives as perspective source for receiving therapeutic agents to be used in a combined therapy
for primary and metastatic brain tumors Anyhow the mechanism of caffeine interaction was not
clear To provide the proper understanding of caffeine action the precise structural data are
necessary To increase the accuracy of the structural date and to simulate the interaction of caffeine
with tetraoxidoanion and hydration water molecules the synthesis of caffeine cobalt hexahydrate
perrhenate was carried out from saturated water solutions and the single crystal thus obtained were
subjected to X-ray structural study at Bruker KAPPA APEX II diffractometer
Supramolecular interactions of caffeine molecules with each other water molecules and oxygen
atoms of tetraoxidoanions as in a new compound of Co(H2O)6[ReO4]2 caffeine are analyzed in
these study through comparison of the new precise structural data with quantum chemical analyses
The reasons for alterable orientation of caffeine molecules to each other and for the H-bonds
network formation has been evaluated
1 Vartanyan LP Kolesova MB Gornaeva GF Pustovalov YuI Caffeine derivatives mdash
perspective method of the search for anticancer and radiomodifying drugs in combined therapy
for malignant brain tumors Psychopharmacol Biol Narcol mdash 2005 mdash Vol 5 N 4 mdash P
1093ndash1095 Central Research Institute of Roentgenology and Radiology Saint Petersburg
154
P43
EFFICIENT CONVERSION OF ALKENYNONES TO 2-
METHYLENEDIHYDROPYRROLONES
PR Golubev AS Pankova
St Petersburg State University Institute of chemistry St Petersburg Russia
Earlier we have developed a method for the synthesis of cross-conjugated ketones 2 and
investigated their interaction with common binucleophiles ndash hydrazines and amidines [12] Our
next goal was to study the reaction of enynones 2 with amines
It was shown earlier [12] that the ethoxymethylene group is the most active center of ketones 2 in
reactions with nucleophiles In line with this enamines 3 were obtained on the first stage in
reactions with amines Various solvents were used successfully in this reaction but diphenyl ether
was considered to be the most convenient since in this case both synthetic steps could be performed
in a one-pot fashion without isolation of intermediate enamines 3
We proposed that thermolysis of enamines 3 could lead to their cyclization via Michael-type
intramolecular addition of amine nitrogen atom to a triple bond We have found that this reaction
proceeds smoothly at 200 degC as a 5-exo-dig cyclization leading to pyrrolinones 4 as single products
in good to excellent yields Various amines with alkyl aryl or heteroaryl substituents were used
Thus monoalkylamines are predictably the most active coupling partners but in this case steric
factors play a crucial role Nevertheless even tert-butylamine was employed successfully in this
reaction along with n-alkyl- and (hetero)benzylamines In case of anilines the reaction outcome was
fully consistent with nucleophilicity of the amine used Generally anilines with electron-donating
substituents reacted more readily and provided higher yields than electron-deficient ones and a
slight decrease of yield was observed when para-substituted aniline was replaced with an
ortho-substituted analogue Finally pyrrolidinones 4 with various heteroaromatic substituents at
nitrogen atom can also be obtained
In conclusion we offer a straightforward and high-yielding method for the synthesis of previously
unknown 2-methylenedihydropyrrolones
[1] AS Pankova PR Golubev IV Ananyev MA Kuznetsov Eur J Org Chem 2012 30
5965-5971
[2] PR Golubev AS Pankova MA Kuznetsov Eur J Org Chem 2014 17 3614-3621
Authors thank the Russian Scientific Fund for a research grant No 14-13-00126
155
P44
THEORETICAL INVESTIGATION OF PALLADIUM-CATALYZED
DIMERIZATION OF ALKYNES HYDROPALLADATION VS
CARBOPALLADATION PATHWAYS
EG Gordeev VP Ananikov
ND Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences
Catalytic dimerization of terminal alkynes is a waste-free process that allows preparation of enynes
within atom-economic transformation The key question for practical utilization of the dimerization
approach is to understand the factors responsible for rendering regioselective transformation and
lead in a to a single poduct
The studied catalytic dimerization of terminal alkynes may involve two mechanisms
hydropalladation and carbopalladation which results in two types of products - head-to-head and
head-to-tail dimers Experimentally it has been found that the presence in the reaction mixture of
carboxylate anion direct the reaction to head-to-tail product only [1] To reveal the mechanistic
picture we have carried out the quantum-chemical modeling (B3LYP6-311G (d) amp SDD) of the
catalytic dimerization of phenylacetylene including participation of the carboxylate anion
Theoretical calculations have shown that in the absence of carboxylate anion the reaction proceeds
as hydropalladation and forms head-to-head product since potential barrier of the hydropalladation
rate-determining step is much smaller than the barrier of the carbopalladation rate-determining step
The predominant formation of head-to-head product was also determined by kinetic factor the
energy of the corresponding transition state was smaller as compared to the transition state of
carpbopalladation pathway
When carboxylate anion (acetate ion was used for modeling) was added to the reaction mixture the
H lignad at the metal center was blocked that and only carbopalladation pathway become possible
Indeed coordination of the carboxylate ion to the palladium atom leading to the formation of the
ion pair destabilized head-to-head intermediate complex As a result the second phenylacetylene
molecule was not able to enter into the metal coordination sphere In the case of head-to-tail
intermediate complex such destabilization did not take place
Theoretical study of complete potential energy surface and comparison with experimental data will
presented and discussed
References [1] Zatolochnaya OV Gordeev EG Jahier C Ananikov VP Gevorgyan V Carboxylate
Switch between Hydro- and Carbopalladation Pathways in Regiodivergent Dimerization of
Alkynes Chem Eur J 2014 DOI 101002chem201402809
Acknowledgement Cooperation with V Gevorgyan (UIC Chicago) and his group is greatly
acknowledged in this project The support of the Russian Foundation for Basic Research (RFBR 14-
03-31752) is gratefully acknowledged
156
P45
CROSS-METATHESIS OF POLYNORBORNENE AND POLY(1-
OCTENYLENE) AS A NEW ROUTE TO NORBORNENE AND
CYCLOOCTENE MULTIBLOCK COPOLYMERS
ML Gringolts YuI Denisova GA Shandryuk LB Krentsel AD Litmanovich YaV
Kudryavtsev ESh Finkelshtein
AV Topchiev Institute of Petrochemical Synthesis Russian Academy of Sciences Russia
Norbornene (NB) and cyclooctene (COE) are well-known objects in ring-opening metathesis
polymerization (ROMP) Their homopolymers synthesized by ROMP are important commercial
products [1] Polynorbornene (PNB) which is sold under the trademark Norsorex has various
special applications Poly(1-octenylene) (PCOE) known as Vestenamer or polyoctenamer
possesses unusual properties for an elastomer At the same time the ROMP synthesis of NB-COE
copolymers is rather difficult because of considerably different polymerization activities of the
comonomers This problem can be solved by catalyst modification [2] or using NB with
substituents decreasing its activity [3]
We propose a new approach to the synthesis of NB-COE multiblock copolymers via interchain
cross-metathesis of PNB and PCOE That approach enabled us to obtain new copolymers using the
1st generation Grubbsrsquo catalyst Cl2(PCy3)2Ru=CHPh which is not suitable for copolymerization of
NB and COE
+[R u = C H P h ]
6n ba c
mC O E - C O E
P C O E
N B - N B
P N B
N B -N B N B -C O E C O E -C O E
C H C l3
Cross-metathesis between PNB and PCOE has been successfully realized New NB-COE
multiblock copolymers were identified and characterized by NMR spectroscopy GPC and DSC
methods It was found that in the course of the reaction the average lengths of PNB and PCOE
blocks were decreased as well as the copolymer molecular weight and crystallinity For copolymer
of 11 composition Tg is about -30 oC which is higher than for PCOE (- 80
oC) and lower than for
PNB (39 o
C) The exchange degree (conversion) reached approximately 40-50 in 24 h
Copolymer characteristics can be controlled by varying concentration of the catalyst
The work was supported by RFBR (project 14-03-00665)
1 KJ Ivin JC Mol (1997) Olefin Metathesis and Metathesis Polymerization Academic Press
London
2 Marc Bornand und Peter Chen Angew Chem 2005 117 8123 ndash8125
3 CS Daeffler and RH Grubbs Macromolecules 2013 46 3288minus3292
157
P46
SELECTIVE C=O HYDROGENATION OF ENONES ENALS AND
ENOATES
DG Gusev D Spasyuk
Wilfrid Laurier University Department of Chemistry Waterloo Canada
In the past three years1-4
we developed catalysts 1 - 3 for the reduction of esters under hydrogen
gas Complexes 2 and 3 are todayrsquos most efficeint catalysts for this process and have recently
become commercially available (Aldrich catalogue numbers 746339 and 746347)
Here we disclose the synthetic structural and catalytic details of our newest robust practical and
efficient H2 hydrogenation catalyst distinguished by excellent carbonyl selectivity The air-stable
osmium complex from our laboratory OsHCl(CO)(NNNP-tBu) (4) is todays most successful
general catalyst for production of unsaturated alcohols from enals enones and alkyl enoates under
H2 at 25 - 100 degC while using 001 - 005 mol [Os] preferably without solvent
References
1 Goussev D G Spasyuk D PCT Patent Application WO 2013023307 A1
2 Spasyuk D Smith S Gusev D G Angew Chem Int Ed 2013 52 2538 - 2542
3 Spasyuk D Gusev D G Organometallics 2012 31 5239-5242
4 Spasyuk D Smith S Gusev D G Angew Chem Int Ed 2012 51 2772-2775
158
P47
OVERCOMING SELF-DESTRUCTIVE REACTIVITY IN
ORGANOLANTHANIDE COMPLEXES
PG Hayes KRD Johnson BL Kamenz
University of Lethbridge Department of Chemistry Lethbridge Canada
In an effort to prepare organometallic lanthanide complexes that feature new and unusual
properties we have designed and synthesized several families of pincer ligands comprised of
phosphinimine donors attached to rigid aromatic cores Rare earth complexes of the ligands have
been prepared and notably diverse reaction behavior such as cyclometalative CndashH bond activation
dearomatization and functionalization of ligand pyrimidine rings by 15-alkyl migration and ring-
opening insertion has been observed Notably the evolution of the design of these pincer ligands
has recently yielded a series of thermally stable organolanthanide species that are resistant to
cyclometalation The synthesis as well as the reaction chemistry of the corresponding
organometallic complexes will be presented
159
P48
METALLOPORPHYRIN-INCORPORATED DIPHOSPHINE LIGANDS FOR
METAL ION-BINDING
G-A Yu K-M Wong J-S Huang N Zhu C-M Che
The University of Hong Kong Department of Chemistry Hong Kong
Diphosphine ligands have been widely used in organometallic chemistry and catalysis1 By
incorporation of functional units such as metallomacrocycles the resulting functionalized
diphosphines could exhibit unusual properties or binding behavior In this study we prepared
several examples of ruthenium porphyrin phosphine complexes [RuII(Por)(dppm)2] (1 Por = TTP
4-MeO-TPP F20-TPP dppm = bis(diphenylphosphino)methane) by a similar method to that
previously reported for their congeners2 Reaction of complexes 1 with a number of metal
complexes MLn afforded [(LmM)( -dppm)RuII(Por)( -dppm)(MLm)] (2 M = Ag Au) which have
been characterized by spectroscopic methods including 1H NMR
31P NMR and UVVis
spectroscopy and also by X-ray crystal structure determination The formation of complexes 2 from
complexes 1 demonstrates the role of complexes 1 as a unique type of diphosphine ligands
functionalized with metalloporphyrins (which constitute a large family of metal complexes that
resemble heme cores in biological systems and exhibit a wide variety of applications3) Studies are
underway to explore the properties of this new type of metalloporphyrin-incorporated diphosphine
complexes of transition metals
References
1 (a) Genet J-P Ayad T Ratovelomanana-Vidal V Chem Rev 2014 114 2824 (b) Broda
H Hinrichsen S Tuczek F Coord Chem Rev 2013 257 587 (c) Birkholz M-N Freixa
Z van Leeuwen P W N M Chem Soc Rev 2009 38 1099 (d) Freixa Z van Leeuwen P
W N M Coord Chem Rev 2008 252 1755 (e) Tuczek F Adv Inorg Chem 2004 56 27 (f)
Bessel C A Aggarwal P Marschilok A C Takeuchi K J Chem Rev 2001 101 1031
2 Ball R G Domazetis G Dolphin D James B R Trotter J Inorg Chem 1981 20 1556
3 (a) Handbook of Porphyrin Science Kadish K M Smith K M Guilard R Eds World
Scientific 2010 (b) The Porphyrin Handbook Kadish K M Smith K M Guilard R Eds
Academic Press 2000
160
P49
SYNTHESIS OF NOVEL ACCEPTOR MOLECULES OF MONO- AND
MULTIADDUCT FULLERENE DERIVATIVES FOR IMPROVING
PHOTOVOLTAIC PERFORMANCE
HB Liu C Liu
Institute of Chemistry Chinese Academy of SciencesCAS Key Laboratory of Organic Solids
Beijing PR China
Fullerene derivatives are extensively used in organic photovoltaics (OPVs) because of their high
electron affinity and high mobility1 and remarkable properties on photoinduced electron transfer in
which [66]-phenyl C61-butyric acid methyl ester (PC61BM) is the most widely employed material2
We have successfully synthesized and separated a series of tert-butyl 4-C61-benzoate (t-BCB)
organofullerenes including monoadduct diadduct and triadduct compounds and investigated their
photophysics electrochemistry thermal properties and high-performance liquid chromatography
analysis3 The photovoltaic devices were fabricated based on monoadduct diadduct and triadduct
products and the devices based on them exhibited power conversion efficiencies of 243 048
and 168 respectively Methyl 4-C61-benzoate series fullerene materials with low cost and high
yield including monoadduct and bisadduct compounds were also synthesized and the photovoltaic
devices based on them showed power conversion efficiency of 348 and 016 respectively4 This
was the first time to study the dependent relationship on the device performance and the different
isomer numbers This work supplied new route to design fullerene materials as PCBMrsquos alternative
References
1 Yu G Gao J Hummelen J C Wudl F Heeger A J Science 1995 270 1789
2 Liu C Xiao S Shu X Li Y Xu L Liu T Yu Y Zhang L Liu H Li Y ACS Appl
Mater Interfaces 2012 4(2)1065
3 Liu C Xu L Chi D Li Y Liu H Wang J ACS Applied Materials amp Interfaces 2013 5
1061
4 Liu C Li Y J Chi D Chen S H Liu T F Wang J Z Liu H B Li Y L Fullerenes
Nanotubes and Carbon Nanostructures 2014 22 277
161
P50
THE FIRST EXAMPLE OF THE SYNTHESIS AND STUDY OF 2-[(Z)-1-
(FERROCENYLMETHOXY)PROP-1-ENYL]-5-ETHENYLIDENE-45-
DIHYDRO-13-THIAZOLES BY METHOD OF MALDI MASS
SPECTROMETRY
OV Inozemtseva OA Tarasova NA Nedolya LV Klyba ER Sanzheeva BA Trofimov
A E Favorsky Irkutsk Institute of Chemistry Siberian Branch of the Russian Academy of Sciences
1 Favorsky St Irkutsk 664033 Russian Federation
Earlier unknown 2-[(Z)-1-(ferrocenylmethoxy)prop-1-enyl]-5-ethenylidene-44-dimethyl-45-
dihydro-13-thiazole (1) the first representative of ferrocenyl-substituted functionalized 2-
thiazolines was obtained in two preparative steps from (ferrocenylmethoxy)allene isopropyl
isothiocyanate and propargyl bromide (through synthesis and structural reorganization of
conjugated 2-aza-135-triene 2 under action of t-BuONa) in 33 yield (not optimized)
It was shown that the matrix-assisted laser desorptionionization (MALDI) mass spectrometry can
be appropriate for the study of the low molecular weight thiazoles in particular such as compound
1 (with 25-dihydroxybenzoic acid as a matrix) In the gas phase under the experiment conditions
the generation of [2M] and [2M ndash H2O] ions (M is molecule of thiazole 1) was detected The
analysis of the fragmentation of these ions in field-free region showed that their decay was mainly
due to both the degradation of thiazole ring and the formation of the ion [FcCH2]+ at mz 199
Mass spectrum MALDI (under the positive mode) of thiazole 1 registered in the mode reflectron
On the inserts А ndash the МS2 spectrum of ion at mz 768 B ndash the МS
2 spectrum of ion at mz 786
The authors are grateful for the financial support from the Russian Foundation for Basic Research
(Grant No 13-03-00691a)
786182
768312
784186
0
1000
2000
3000
4000
5000
Inte
ns [a
u]
7675 7700 7725 7750 7775 7800 7825 7850 7875 7900mz
199044
768338
473156313149
000
025
050
075
100
1254x10
Inte
ns [a
u]
200 400 600 800mz
2M - H2O
2M
A
786469
199130
473353313201 6433920
1
2
3
4x10
Inte
ns [a
u]
200 400 600 800mz
B
162
P51
SYNTHESIS AND MASS SPECTRA OF ELECTRON AND CHEMICAL
IONIZATION OF 2-[(Z)-1-METHOXYPROP-1-ENYL]-5-ETHENYLIDENE-
45-DIHYDRO-13-THIAZOLE
OV Inozemtseva LV Klyba ER Sanzheeva NA Nedolya OA Tarasova BA Trofimov
A E Favorsky Irkutsk Institute of Chemistry Siberian Branch of the Russian Academy of Sciences
1 Favorsky St Irkutsk 664033 Russian Federation
The behavior of 2-[(Z)-1-methoxyprop-1-enyl]-5-ethenylidene-45-dihydro-13-thiazoles 1ndash4
synthesized for the first time from methoxyallene isothiocyanates and propargyl bromide1 under
electron ionization (EI 70 eV) and positive ion chemical ionization (PICI methane) has been
studied
Principal fragmentation routes of the 45-dihydro-13-thiazoles 1ndash4 after EI include a thiazole ring
cleavage (pathway 1) and the loss of alkyl substituent mainly at position 4 (pathway 2)
For PICI of the compounds 1ndash4 are typical processes of protonation and electrophilic addition
followed by the loss of the 2-methoxybut-2-enenitrile molecule
The authors are grateful for the financial support from the Russian Foundation for Basic Research
(Grant No 13-03-00691a)
1 Nedolya N A Tarasova O A Albanov A I Trofimov B A Tetrahedron Lett 2014 55
2495ndash2498
163
P52
FLUORESCENCE PHOTOSENSITIVE MATERIALS FOR INFORMATION
OPTICAL RECORDING
VF Traven IV Ivanov SM Dolotov DA Cheptsov
D Mendeleev University of Chemical Technology of Russia
In the modern world computer and information technology continue to develop with increasing
speed that increases the requirement for higher performance systems that are capable of
preservation reproduction and processing of information at very high speeds An actively
developing area allowing to obtain a carrier with high density recorded information is to
manufacture fluorescent multilayer disks (FMD) Use of the information recording FM-discs is
based on photochemical conversion of compounds that change their fluorescent properties whether
it is shift of the maximum fluorescence appearance of fluorescence or its attenuation [1]
N N
R 1
R 3
R 2
h
C C l4
N N
R 1
R 3
R 2
+ H+
O
O
O
N
C H 3
C H 3
N
C H 3
CH 3 O
O H
O
N+
C H 3
C H 3
N
C H 3
CH 3
H+
Previously we have studied new reaction photodehydrogenation 3-pyrazolinylcoumarines and
found it be accompanied by increased acidity [2] In this report we consider an application of this
reaction for opening of the lactone form of rhodamine dye These two reactions are accompanied by
the formation of the fluorophore with a high fluorescence quantum yield and high light resistance
As we have found both these reactions undergo easily both in organic solvents and in polymer
matrixes For example the irradiation of the polymethylmethacrylate film which contain dissolved
pyrazoline hexachloroethane and lactone of Rhodamine B by light in a wavelength range of 360-
400 nm leads to the appearance coloration of the film with irradiated areas exhibits fluorescent
properties We have used these results for optical data recording with fluorescent readout [3]
1) C M Rudzinski DG Nocera In Optical Sensors and Switches KS Schaze Ed Marcel
Dekker New York USA 2001 (Chap 1)
2) IV Ivanov SM Dolotov OI Kobeleva TM Valova V A Barachevskii VF Traven
IzvRAN Serkhim 2012 2290-2300
3) V F Travenacute S M Dolotov I V Ivanov V A Barachevsky O I Kobeleva T M Valova I
V Platonova A O Ait Patent application no 3011109935 of March 17 2011
164
P53
RING OPENING OF DONOR-ACCEPTOR CYCLOPROPANES WITH
AZIDE ION ndash STRAIGHTFORWARD ACCESS TO AZA-HETEROCYCLES
KL Ivanov EV Villemson EM Budynina OA Ivanova IV Trushkov
Moscow State University Department of Chemistry Moscow Russia
Nucleophilic ring opening of donor-acceptor (DA) cyclopropanes is an efficient approach to various
polyfunctional structures including natural products and medicines1-4
Currently a wide range of
nucleophiles was introduced into reactions with DA cyclopropanes however a number of
nucleophilic reagents still remains unexplored In this research we have found optimal conditions
for DA cyclopropanes 1 ring opening with azide ion leading to the formation of -azidocarbonyl
compounds 2 Moreover we developed one-pot process consisting of ring openingKrapcho
dealkoxycarbonylation which allowed us to achieve a simple approach to the GABA precursors 3
The concurrent presence of azide function activated methine or methylene group EDG and EWG
substituents in compounds 2 and 3 makes them convenient building blocks for the streamlined
synthesis of wide range five- and six-membered N-heterocyclic frameworks which are ubiquitous
structural units of numerous natural and synthetic bioactive molecules We designed approaches to
pyrrolidones pyrroles piperideines triazolopyridines tetrazolopyridines etc based on simple
synthetic sequences including Staudingeraza-Wittig cascade or [3+2] cycloaddition as key steps
These strategies were successfully used in formal syntheses of nicotine and atorvastatin
1 Reissig H-U Zimmer R Chem Rev 2003 103 1151-1196
2 Carson CA Kerr MA Chem Soc Rev 2009 38 3051-3060
3 Cavitt MA Phun LH France S Chem Soc Rev 2014 43 804-818
4 Schneider TF Kaschel J Werz DB Angew Chem Int Ed 2014 53 5504-5523
165
P54
NATURAL GAS HYDRATE FORMATION IN THE PRESENCE OF
SURFACTANTS
IK Ivanova1 ME Semenov
2 II Rozhin
2
1 - Ammosov North-Eastern Federal University
2 - Institute of Oil and Gas Problems Siberian Branch Russian Academy of Sciences
The aim of the work is determination of the temperature and pressure of formation and
decomposition (melting) of the natural gas hydrate synthesized from natural gas of the Sredneviluy
gas and condensate field (GCF) and distilled water also in the systems based on it in the presence
of sulfonic of 01 by weight as well as with artificial nucleating agent (sand) by differential
scanning calorimetry
Fig 1 Calculated equilibrium conditions of the gas hydrate formation for natural gas of the
Sredneviluy GCF and methane
The experimental data (Fig 1) are identical to those calculated by the method of E Dendy Sloan for
the used natural gas hydrate equilibrium conditions It should be noted that against the background
stands out experimental points obtained by the decomposition of natural gas hydrate which was
synthesized from a 01 solution of sulfonic Comparing the equilibrium conditions of the
individual components of natural gas it is found that this point corresponds to the equilibrium
conditions of the methane hydrate It is known that natural gas hydrates are a mixture of hydrates of
different gases with complex structure This study suggests the possibility of separation of this
mixture on the hydrates of individual gases Furthermore it was found that the use of surfactants
leads to an increased conversion of water into the gas hydrate (gt 70) compared with 23 of the
gas hydrate formation in distilled water
166
P55
CONTROL OF THE REACTION SELECTIVITY IN Pd AND Ni-
CATALYZED HYDROPHOSPHORYLATION OF ALKYNES
JV Ivanova1 LL Khemchyan
1 SS Zalesskiy
1 VP Ananikov
1 IP Beletskaya
2 ZA Starikova
3
1 - Zelinsky Institute of Organic Chemistry RAS Moscow Russia
2 - Lomonosov Moscow State University Chemistry Department Moscow Russia
3 - Nesmeyanov Institute of Organoelement Compounds RAS Moscow Russia
Nowadays transition-metal-mediated carbon-heteroatom (C-E E=S Se Si P Te O) bond
construction has drawn great attention due to well-recognized advantages high selectivity
quantitative yields and mild reaction conditions [1][2][3] The study of metal-catalyzed
phosphorus-carbon (P-C) bond formation has led to significant progress in organic synthesis and
established numerous synthetic procedures for the synthesis of new valuable compounds [1]
We developed two switchable synthetic protocols allowing us to obtain the products of choice via
subtle change in the catalytic system (Scheme 1) The palladium-based catalyst demonstrated high
sensitivity to the number and position of substituent in the aromatic rings of the phosphine ligand
Application of two different phosphines selectively directed the catalytic reaction either to linear or
branched product formation [4] The Ni(acac)2DIBAL-H precatalyst was the first example of
nickel-based system which allowed to synthesize vinylphosphonates bisphosphonates or
alkyltetraphosphonates without any ligands or solvents [5][6] Slight variations of Ni precatalyst
loading routed the selectivity of the hydrophosphorylation reaction Mechanistic study with ESI-MS
and NMR methods revealed the key nickel intermediates involved into the catalytic cycle [6]
Scheme 1
[1] VP Ananikov M Tanaka (Eds) Hydrofunctionalization Springer 2013 Heidelberg ISBN
978-3-642-33734-5 DOI 101007978-3-642-33735-2
[2] IP Beletskaya VP Ananikov Chem Rev 2011 111 1596
[3] F Alonso IP Beletskaya M Yus Chem Rev 2004 104 3079
[4] VP Ananikov JV Ivanova LL Khemchyan IP Beletskaya Eur J Org Chem 2012
3830
[5] YuV Ivanova LL Khemchyan SS Zalesskii VP Ananikov IP Beletskaya Rus J Org
Chem 2013 49 1099
[6] LL Khemchyan JV Ivanova SS Zalesskiy VP Ananikov IP Beletskaya ZA Starikova
Adv Synth Catal 2014 356 771
167
P56
Cu-CATALYZED AEROBIC OXIDATIVE TRANSFORMATION OF
KETONE-DERIVED N-TOSYL HYDRAZONES A NEW ENTRY INTO
ALKYNES
X-W Li W-Q Wu H-F Jiang
South China University of Technology School of Chemistry and Chemical Engineering
Guangzhou P R China
Alkyne moiety is a fundamental structural element and functional group occurring in various
bioactive molecules functional materials and natural products1 Sonogashira reaction and
electrophilic alkynylation2 are the most widely used methods for the construction of alkynes still
some formidable challenges remained to be resolved3 On the other hand the field of alkyne retro-
hydration that is deprotonation of ketone derivatives for the alkynes synthesis however is still in
its infancy 4
In our continuing efforts toward the development of green chemistry on selective oxidation of
unsaturated hydrocarbons5
we have developed an efficient copper-catalyzed aerobic
dehydrogenation of ketone-derived N-tosyl hydrazones which were carbene precursors to the
corresponding alkynes Further cross-couplings of N-tosyl hydrazones with halides or terminal
alkynes were also performed delivering to functionalized alkynes or asymmertric diynes A
mechanism involved aerobic oxidation of Cu-carbene intermediate was proposed for this C-C triple
bond formation
Reference
1 Modern Acetylene Chemistry Stang P J Diederich F Eds VCH Weinheim Germany
1995
2 Dudnik A S Gevorgyan V Angew Chem Int Ed 2010 49 2096
3 Negishi E Anastasia L Chem Rev 2003 103 1979
4 Negishi E King A O Klima W L Patterson W Silveira A J Org Chem 1980 45
2526
5 Wu W Jiang H Acc Chem Res 2012 45 1736
168
P57
[Co]-СATALYZED [6+2]-CYCLOADDITION OF 12-DIENES TO 1357-
CYCLOOCTATETRAENE
VA Dyakonov1 GN Kadikova
1 GF Gazizullina
2 UM Dzhemilev
1
1 - Federal State Institution of Science Institute of Petrochemistry and Catalysis Russian Academy
of Sciences Laboratory catalytic Synthesys Ufa Russia
2 - Ufa State University of Economics and Service Ufa Russia
Eight-membered carbocycles are found in many natural compounds exhibiting high biological
activity [1] The catalytic cycloaddition based on 1357-cyclooctatetraene (COT) are an effective
method for the synthesis of such carbocycles [2] [Co]-Catalyzed cyclodimerization of COT with
alkynes leading to the formation of bicyclo[422]deca-2479-tetraenes 1 [3]
R
R
C o I2d p p e Z n Z nI
2
4 0 oC C2H
4C l
2
1 It should be noted that in literature have no examples of catalytic codimerization of 1357-
cyclooctatetraene with 12-dienes In the development of this work and our ongoing research [4ab]
we carried out [6π+2π]-cycloaddition of COT with 12-dienes in the presence of 10 mol
CoI2dppeZnZnI2 (C2H4Cl2 40 deg C 20 h) The corresponding bicyclo[422]deca-247-trienes 2
were obtained in high yields
R
RC o I
2d p p e Z nZ nI
2
4 0 oC C2H
4C l
2
2R = P h A lk
This work was performed under financial support from the Russian Foundation for Basic Research
(Grant 13-03-00167 and Grant of RF President (Sci Sh ndash 213620143))
1 Plemenkov VV Introduction to the chemistry of natural compounds Kazan 2001 376 p
2 Yu ZX Wang Y Wang Y Transition-metal-catalyzed cycloadditions for the synthesis of eight-
membered carbocycles Chem Asian J 2010 1072-1088
3 Achard M Mosrin M Tenaglia A Buono G Cobalt (ΙΙ)-Catalyzed [6+2] Cycloadditions of
Cyclooctatetra(tri)ene with Alkynes JOrgChem 2006 71 2907 -2910
4 a) Dyakonov VA Kadikova GN Dzhemilev UM Ti-catalyzed [6π +2 π]-cycloadditions of
allenes with 135-cycloheptatriene Tetrahedron Lett 2011 52 2780-2782 b) Dzhemilev UM
Kadikova GN Kolokoltsev DI Dyakonov VA Catalytic [6π+2π]-cycloaddition of alkynes
12- and 13-dienes to 135-cycloheptatrienes involving Ti complexes Tetrahedron 2013 69
4609-4611
169
P58
MOBILE NANODEFECTS AS COMPLEXING AGENTS IN SOLID PHASE
CHEMISTRY
AM Kaplan NI Chekunaev
NNSemenov Institute of Chemical Physics Russian Academy of Sciences
Put forward by one of the authors the idea about the possible role of mobile nanodefects as
complexing agents allowed to explain for the first time a number of non-trivial effects of solid-
phase chemistry These are 1 the effect of greatly acceleration of catalytic processes induced by
high energy impacts on heterogeneous catalysts [1] 2 the phenomena of freezing of polymer
chains at constant temperatures and reanimation of such chains at temperatures increasing of
investigated samples in solids [2] 3 the effect of exceeding by several orders of the rate of
affiliation of monomer molecules to the active centers in glass monomers samples compared to
crystalline samples of the monomer [3] 4 the phenomenon of the abnormal logarithmic time
dependence of the polymer yield for unterminated solid-state polymerization at low conversions [4]
In contrast to gas and liquid phases very low orientation mobility of microparticles in solid phase
frequently does not allow to perform chemical interaction even particles of reagents which are in
contact with each other for prolonged time This effect is a consequence of unacceptable for
chemical interaction starting mutual orientation of the particles and impossibility to improve the
situation at insufficient space close to them Furthermore structural nanodefects (mobile vacancies
polyvacancies dislocations nanoincontinuity etc) present in the real solid bodies may in case of
their sufficient mobility lead to pair of potentially chemically capable but unreacting due to
orientational immobility of adjacent reagents particles in quite dense areas of solid bodies
sufficient free space Remobing by this the steric barrier for the interactions of such particles
Consequently as it was for the first time mention by the presenter real (lsquolivingrsquo) active center (A)
of solid phase reactions should be considered not the experimentally detectable traditional active
centers (A) (radical and ions) but a peculiar complex of such centers with the carrier of excess of
volume mdash with mobile nanodefects The concentration of [A]ltlt[A] It should be pointed out the
special role of mobility of nanodefects in formation of real cative centers A In case of presence of
in the system of only motionless nanodefects ldquochemicalrdquo diffusion leads in time to the removal of
reacting particles from such defects turming these particles to inactive state In heterogenous
catalysis this effect is similar to the effect of catalyst poisoning Movable nanodefects which
activated during some time a group of reagent particles move to another such group and also
activate it This process of activation of chemical process takes places until meeting of moving
nanodefects leading to sticking of defects and decrease of their concentration Based on concept of
moving nanodefects with excessive free volume as complexing agents authors using computer
calculations in papers [1-4] explained the effects previously considered anomalous mentioned
above
1 AMKaplan VVLunin NIChekunaev Book of abstracts of VII Voevodsky conference
laquoPhysics and Chemistry of elementary chemical processesraquo P 191-192 Chernogolovka 2007
2 AM Kaplan NI Chekunaev Doklady Physical Chemistry Vol 425 Part 1 pp 51-53 2009
3 AM Kaplan NI Chekunaev Russian Chemical Bulletin No 8 pp 677-683 2009
4 AM Kaplan NI Chekunaev Polymer Science Series B Vol 52 No 1-2 pp 57-62 2010
170
P59
SYNTHESIS OF OLIGOSACCHARIDE FRAGMENTS OF CANDIDA
ALBICANS MANNAN CORRESPONDING TO ANTIGENIC FACTOR 6
AA Karelin YE Tsvetkov NE Nifantiev
N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Laboratory of
Glycoconjugate Chemistry Moscow Russia
The yeast-like fungi of the genus Candida are opportunistic pathogenic microorganisms capable of
causing severe infections in immunocompromised patients The main surface antigen of Candida
responsible for its antigenic specificity is mannan which represents the carbohydrate part of the cell
wall mannoprotein The determinants of antigenic factor 6 are represented by several β-D-Man-
(1rarr2)-residues attached to short α-(1rarr2)-linked chains
Here we report synthesis of oligosaccharides 1 and 2 containing two and three β-linked residues
The presence of the amino group in the aglycones of the synthetic oligosaccharides allows their
subsequent covalent binding to high-molecular carriers and labels of various types
We utilized a convergent approach based on glycosylation of known α-(1rarr2)-linked mannosyl
acceptor with β-(1rarr2)-linked donors
The preparation of required donors was started from compound 3 The thiomannoside was
transformed into sulfoxide 4 Then these monosaccharides were coupled to give required
disaccharide donor Here we used the fact that conditions of sulfoxide activation donrsquot affect
thioglycosides Oxidation of dimanosyl donor 5 followed by glycosylation of 3 allowed obtaining
trisaccharide donor 7 Glycosylation of α-(1rarr2)-linked mannosyl acceptor with donors 5 and 7 and
subsequent removal of protecting groups gave target olygomannosides 1 and 2
Acknowledgments
This work was supported by the Russian Foundation for Basic Research under grant 14-03-31583
171
P60
NANOSTRUCTURED NICKEL ORGANOSULFIDES SYNTHESIS
CHARACTERIZATION AND APPLICATION IN THE CATALYTIC
CARBON-SULFUR BOND FORMATION REACTION
AS Kashin VP Ananikov
ND Zelinsky Institute of Organic Chemistry RAS Moscow Russia
Over the last decades nanostructured metal chalcogenides have made an outstanding contribution to
the nanotechnology microelectronics optics and material science However their application in
organic synthesis and catalysis remains largely unexplored [1]
In our work we focused on the nickel organosulfides ndash [Ni(SAr)2]n These nanostructured nickel
complex salts can be easily prepared by the reaction between nickel acetylacetonate and aryl thiols
Rapid ligand substitution accompanied with the self-organization in solution leads to formation of
polymeric structures where nickel atoms are linked by μ2-SAr groups Tuning of the reaction
conditions or changing of the substituent in the aromatic ring of thiol allows to generate [Ni(SAr)2]n
particles of various shapes and sizes (Figure 1)
Figure 1 FE-SEM images of [Ni(SAr)2]n particles Ar = Ph (A) p-BrPh (B)
We have demonstrated that synthesized nickel aryl sulfides can be utilized as a source of SAr
groups for the carbon-sulfur bond formation in the cross-coupling reaction with aryl halides [2]
Reaction in the presence of palladium- or copper-based catalytic system results in the diaryl sulfides
formation with the yield up to 95 (Scheme 1)
Scheme 1 Catalytic C-S bond formation reaction between nickel organosulfides and aryl halides
A unique effect of morphology control of the SAr group donor reactivity in cross-coupling reaction
was found Mechanistic studies have shown that cross-coupling reaction with Cu catalyst proceeds
in the liquid phase and involves leaching whereas the same reaction with Pd catalyst is more
complex and may involve both ndash homogeneous and heterogeneous pathways
[1] VP Ananikov IP Beletskaya Dalton Trans 2011 40 4011
[2] AS Kashin VP Ananikov Top Catal 2013 56 1246
172
P61
SYNTHESIS OF DERIVATIVES OF 6-ACETYL-2-CYCLOHEXENONE AND
THEIR BORON CHELATE COMPLEXES
DS Khachatryan1 II Boyko
2 AA Vardapetyan
1 AL Razinov
1 KR Matevosyan
3
1 - FGU IREA Moscow Russia
2 - ООО TEHNOLOG Pereslavl-Zalessky Russia
3 ndash DI Mendeleev RHTU Moscow Russia
In some cases reactions of enolates obtained using conventional basic reagents (alcoholates
amides metal hydrides) afford products in very low yields12
In the late 70s we first succesfully
used patassium carbonate in Michael reaction for the synthesis in preparative quantities of
derivatives of 2-cyclohexenone 2-4
ndash synthons for construction of physisologically active molecules
including steroids1
The present work follows the studies in the field of synthesis of new derivatives of 2-cyclohexenone
by Michael reaction in the presence of patassium carbonate Of special interest are derivatives of 2-
cyclohexenone containing acetyl substituent in position 6 ndash analogues of 13-diketones which can
complex transition and rear yearth metals 5-7
We studied prepartion of 35-disubstituted 6-acetyl-2-cyclohexenones based on cyclocondensation
reaction of acetylacetone (1) with αβ-unsaturated ketones 2а-h in the presence of catalytic amount
of patassium carbonate at reflux in different solvents
M e M e
O OR
1R
O
R1
O
R
O
M e
M e
O
O O
M e
R1
R
+
1 2 a -h 3 a -h 4 a -h а R=MeOC6H4CH=CH R
1=MeOC6H4 b R=R
1=Ph c R=2-тиенил R
1=Ph
d R=24-Cl2C6H3CH=CH R1=BuOC6H4 e R=4-BuOC6H4CH=CH R
1=4-BuOC6H4
f R=4-AmOC6H4CH=CH R1=4-AmOC6H4 g R=4-lC6H4CH=CH R
1=4-ClC6H4
h R=4-MeC6H4CH=CHR1=4-MeC6H4
In 1Н NMR spectra of all diketones 4a-h the doubling of all expected signals is observed that as
known7 is due to keto-enol tautomerism ie 6-acetyl-2-cyclohexenones behave in solution as
classic 13-diketones
Based on these data the chelating ability of compounds 4a-h was evaluated It was shown that they
can form chelate complexes with boron ndash 13-dioxaborines which possess photosensibilizing
properties5 as well as (with compound 4b as an example) complexes with metals (Сu
2+ Ni
2+ Со
2+
Еu3+
) 46
1 ED Bergmann DGinsburg RPappo in Organic Reactions v10 Wiley New York 1959
2 NMMorlyan DS Khachatryan ShO Badanyan Arm Chem J 1978 31 (2) 866
3 DS Khachatryan AA Vardapetyan GA Panossian RG Mirzoyan NM Morlyan ZhOrH 1990 26
(10) 2092
4 DS Khachatryan AA Vardapetyan VN Tkachenko NM Morlyan Proc Conf laquoIII All-Union
Conference on Chemical reagents Ashgabat 1989 p 107
5 II Boyko TI Boyko AA Vardapetyan GV Nowicka DS Khachatryan NM Morlyan and KK
Koshelev As1704446 USSR Bull Izobr 2000 9
6 VIZelenov Russian JGenChem 200979 (1) 142
7 JKFGeirsson ADGudmundsdottir Synthesis 1990 11 993
173
P62
TRITERPENOID SAPONINS FROM THE ROOTS OF
ACANTHOPHYLLUM GYPSOPHILOIDES REGEL AS POTENTIAL
IMMUNE-MODULATING TOOLS FOR DENDRITIC VACCINE DESIGN
EA Khatuntseva1 VM Menrsquoshov
1 AS Shashkov
1 YE Tsvetkov
1 RN Stepanenko
2 R Ya
Vlasenko2 EE Shults
3 GA Tolstikov
3 TG Tolstikova
3 DS Baev
3 VA Kaledin
4 NA
Popova4 VP Nikolin
4 PP Laktionov
5 AV Cherepanova
5 TV Kulakovskaya
6 EV
Kulakovskaya6 NE Nifantiev
1
1 - N D Zelinsky Institute of Organic Chemistry RAS Leninsky pr 47 Moscow RF
2 - Institute of Immunology Ministry of Health and Social Development of RF Kashirskoe Ch
242 Moscow RF
3 - N N Vorozhtsov Novosibirsk Institute of Organic Chemistry Siberian Branch of RAS pr Acad
Lavrentrsquoeva 9 Novosibirsk RF
4 - Institute of Cytology and Genetics Siberian Branch of the RAS 10 pr Acad Lavrentrsquoeva
Novosibirsk RF
5 - Institute of Chemical Biology and Fundamental Medicine Siberian Branch of the RAS 8 pr
Acad Lavrentrsquoeva Novosibirsk RF
6 - G K Skryabin Institute of Biochemistry and Physiology of Microorganisms RAS Pushchino
Despite significant effort the development of effective vaccines inducing strong and durable T-cell
responses against cancer cells has remained a challenge It is anticipated that the main target of
vaccination are dendritic cells the principal antigen presenting cells whose main function is to
identify exogenous structures and present them to naiumlve CD4+ and CD8+ T cells in lymph nodes A
current strategy to enhance the effectiveness of vaccination is to deliver antigens directly to
dendritic cells which are readily accessible within the well-established in vitro procedure Anti-
cancer dendritic vaccines are intended to activate cytotoxic antigen-specific CD8+ T cells which are
activated via complexes with MHC class I molecules of DCs with the only possibility of
exogenous antigen presentation on those to be done by cross-presentation This process includes
translocation of the antigen from the endosome to the cytosol and is known to be efficiently
promoted by saponins which are part of saponin-based adjuvants QS21 and ISCOMATRIX
Amphiphilic nature of most saponins enables the formation of nano-sized micelles and among
them immune-stimulating complexes (ISCOM) which are currently used as adjuvant systems
These particles are known to be readily engulfed by DCs and the optimal uptake of this type of
vesicles by DCs was reported to be achieved when particle size is 05 ndash 5 μm which corresponds to
conventional size of saponin-based micelles in water solutions
The objective of the present work was to isolate new individual saponins from readily available
routs of Acanthophyllum gypsophiloides with the view to further investigation of their vesicle
formation potential and in vitro effect of saponin-containing ISCOM s on dendritic cells
1 R = OH 2 R = H
Two new triterpenoid saponins 1 and 2 were isolated from the methanol
extract of the roots of Acanthophyllum gypsophiloides Regel These sapo-
nins have quillaic acid or gypsogenin moieties as aglycon and both bear
similar sets of two oligosaccharide chains which are trisaccharide -L-
Ara-(1rarr3)-[ -D-Gal-(1rarr2)]- -D-GlcA and pentasaccharide -D-Xyl-
(1rarr3)- -D-Xyl-(1rarr3)- -L-Rha-(1 2)-[ -D-Qui-(1rarr4)]- -D-Fuc
connected to C-28 The structures were elucidated by the combination of
mass spectrometry and 2D NMR spectroscopy methods Reference EA Khatuntseva et al Beilstein J Org Chem 20128763-75
174
P63
NMR SPECTROSCOPY AND ESI-MS AS EFFECTIVE RAPID METHODS
FOR MONITORING BIOMASS CONVERSION INTO 5-HMF IN IONIC
LIQUIDS
EA Khokhlova VV Kachala VP Ananikov
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
Unprecedented selectivity for biomass and cellulose conversion to 5-HMF has opened outstanding
opportunities for sustainable chemical industry 5-HMF was identified as a platform chemical for
production of biofuels solvents resins liquid alkanes (C7 - C15) and monomers for plastics
However in spite of complete conversion more detailed studies have shown moderate product
yields (40-60) and later formation of by-products (humins) has been identified The main
stumbling block to studying cellulose processing in ionic liquids is the absence of an analytic tool
for monitoring reaction yields in ionic liquids[1]
Our research has been focused on real-time carbohydrate conversion monitoring using a new NMR
based approach for quantitative measurements A practical application of the developed approach
was demonstrated directly in the NMR tube Our latest study revealed the ways to characterize
molecular transformations in IL systems and to detect reaction intermediates using a special reactor
that eliminates microheterogeneity[2] Transformation of carbohydrates to 5-HMF with various
promoters was investigated and discrepancy between conversions and yields was observed High-
quality NMR spectra suitable for integration of individual signals were measured after removing the
intrinsic heterogeneity of ionic liquid samples below the spectroscopic detection level
Moreover we have disclosed a new opportunity of using the MS2 mode in reaction monitoring
frameworks that make it possible to obtain both qualitative and quantitative information A
combined use of the developed NMR and mass spectrometry approaches for analyzing components
of IL solutions will expand the frames of promising chemistry in ILs
[1] VPAnanikov Chem Rev 2011 111 418
[2] EAKhokhlova VVKachala VPAnanikov ChemSusChem 2012 5 783
175
P64
Rh(III) CATALYZED SYNTHESIS OF ISOQUINOLINE DERIVATIVES BY
ANNULATION OF BENZYLAMINES WITH ALKYNES
D-S Kim C-H Jun
Yonsei University Department of Chemistry Seoul Korea
Rh(III)-catalyzed C-H bond cleavage is one of efficient ways to make N-heterocyclic compounds1
In particular ortho-alkyl- or alkenylation provides an efficient synthetic method for preparing
ortho-substituted aromatic ketones2 During the course of our studies on the Rh(III)-catalyzed N-
annulation reaction we found synthetic method of pyridine derivatives from primary allylamines
with alkynes3 In this poster we report a new protocol for the preparation of isoquinoline from
benzylamine and internal alkyne using Rh(III)-catalyst with Cu(II) as an oxidizing agent For
example the N-heterocyclic annulation reaction of 2-methoxybenzylamine with 4-octyne was
carried out at 100 oC for 4 hours in the presence of [Cp
RhCl2]2 (25 mol [Rh]) and
Cu(OAc)2H2O to produce corresponding pyridine in 92 yield The proposed mechanism of this
annulation reaction is also discussed4
1 Song G Wang F Li X Chem Soc Rev 2012 41 3651-3678
2 Murai S Kakiuchi F Sekine S Tanaka Y Kamatani A Sonoda M Chatani N Nature
1993 366 529-531
3 Kim D-S Park J-W Jun C-H Chem Commun 2012 48 11334-11336
4 Kim D-S Park J-W Jun C-H Adv Synth Catal 2013 355 2667-2679
176
P65
A NOVEL BRANCHED MONOSACCHARIDE 36-DIDEOXY-4-C-[(S)-12-
DIHYDROXYETHYL]-D-XYLO-HEXOSE FROM A POLYSACCHARIDE
OF A BACTERIUM OF THE GENUS PHOTORHABDUS
NP Arbatsky1 AS Shashkov
1 NA Kirsheva
2 AN Kondakova
1 RZ Shaikhutdinova
2 SA
Ivanov2 AP Anisimov
2 YA Knirel
1
1 - N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
2 - State Research Center for Applied Microbiology and Biotechnology Obolensk Moscow Region
Russia
The genus Photorhabdus from the family Enterobacteriaceae includes three species of
entomopathogenic bioluminescent bacteria Photorhabdus temperata Photorhabdus luminescens
and Photorhabdus asymbiotica They all have a mutualistic relationship with entomophagous
nematodes from the family Heterorhabditis
These bacteria synthesize an S-form
lipopolysaccharide which consists of lipid A core oligosaccharide and O-specific polysaccharide
(O-antigen) and is important for both pathogenicity and symbiosis Recently aiming at creation of
the chemical basis for classification of Photorhabdus species structures of the O-polysaccharides of
representatives of P asymbiotica subsp asymbiotica and subsp australis1 and P luminescens
subsp laumondii2 have been elucidated In this work we established the O-polysaccharide structure
of P temperata subsp temperata XlNachT and identified a novel branched monosaccharide as its
component
The O-polysaccharide was obtained by mild acid hydrolysis of the lipopolysaccharide isolated from
bacterial cells by phenol-water extraction In addition to monosaccharides that are rather common in
nature (glucose mannose galactose and N-acetylgalactosamine) sugar analysis of the
O-polysaccharide revealed a branched octose called photorhabdose The new sugar was isolated as
a 12rsquo-anhydro furanose derivative by reversed-phase HPLC after full acid hydrolysis of the
O-polysaccharide (Scheme) and its structure as 36-dideoxy-4-C-[(S)-1rsquo2rsquo-dihydroxyethyl]-D-xylo-
hexose was determined by one- and two-dimensional 1H and
13C NMR spectroscopy
Photorhabdose has not been hitherto found in nature and differs from the known branched octoses
36-dideoxy-4-C-[(S)- and (R)-1-hydroxyethyl]-D-xylo-hexoses (yersinioses A and B respectively)
in deoxygenatation of the terminal carbon (C-2rsquo) of the side chain
Scheme Isolation of photorhabdose (Sug) by full acid hydrolysis of the O-polysaccharide Arrows
indicate HH correlations observed in the NOESY spectrum
1 Kondakova A N Kirsheva N A Shashkov A S Shaikhutdinova R Z Arbatsky N P
Ivanov S A Anisimov A P Knirel Y A Carbohydr Res 2011 346 1951-1955
2 Kondakova A N Kirsheva N A Shashkov A S Shaikhutdinova R Z Ivanov S A
Anisimov A P Knirel Y A Carbohydr Res 2012 351 134-137
177
P66
EVOLUTION AND INTERLAYER DYNAMICS OF ACTIVE SITES OF
PROMOTED TRANSITION METAL SULFIDE CATALYSTS UNDER
HYDRODESULFURIZATION CONDITIONS
VM Kogan1 PA Nikulshin
2 NN Rozhdestvenskaya
1
1 - ND Zelinsky Institute of Organic Chemistry RAS Laboratory of catalysis by trasition metals
and their compounds Moscow Russia
2 - Samara State Technical University Samara Russia
According to the suggested dynamic model [1] neighboring layers of the multilayered MoS2
crystallite exchange sulfur between Mo- and S-edges placed one under another in the course of
permanent reductionndashsulfidation processes under hydrogen atmosphere When the sulfur atoms
bonded to Co atoms leave the reduced edge of the layer the atoms of the promoter also move along
the sulfur atoms from one layer to an adjacent layer of higher sulfidation state Then the process
reverses Such oscillations occur until the sulfur organic compound adsorbs on the vacancy on the
reduced edge The frequency of the oscillations determines catalytic activity of the CoMoS slab
Thiophene adsorption makes transfer of a promoter to the neighboring slab improbable because the
electron density of thiophene sulfur compensates the extra positive charge on the Mo atom appeared
after H2S removal When thiophene adsorbs on the vacancy of the CoMoS site the proton linked to
Co moves to the SH group of the neighboring layer forming the H2S which desorbs from this layer
and new vacancy is formed This model explains the reasons of the electron transfer from atom of
promoter to Mo and different locations of the active sites responsible for hydrogenation and
desulfurization on a promoted Mo-sulfide slab A method to evaluate the efficiency of CoMoS
catalysts for HDS of various types of crudes has been developed Now these findings obtain their
explanations within the developed dynamic model (Fig 1)
Fig 1 Dynamic model of
transformations of the active
sites of promoted TMS
catalysts in the course of
thiophene HDS
The suggested model gives a basis to develop criteria to evaluate the efficiency of the catalyst
activity in hydrotreating of various types of crude oil
1 VM Kogan PA Nikulshin NN Rozhdestvenskaya Fuel 100 (2012) 2
178
P67
THE CONCEPT OF INTERLAYER DYNAMICS AND THE MECHANISMS
OF HDS AND ALCOHOL SYNTHESIS ON THE ACTIVE SITES OF
PROMOTED TMS CATALYSTS
VM Kogan1 PA Nikulshin
2 VS Dorokhov
1
1 - ND Zelinsky Institute of Organic Chemistry RAS Laboratory of catalysis by trasition metals
and their compounds Moscow Russia
2 - Samara State Technical University Samara Russia
A new mechanistic model for molybdenum sulfide catalysts with cobalt and nickel promoters under
hydrodesulfurization (HDS) reaction conditions is proposed that includes dynamic migration of
sulfur and promoter atoms between adjacent sulfide layers [12] These migrations are caused by
heterolytic dissociation of gas-phase hydrogen and formation of hydride hydrogen on a promoter
atom Hydride hydrogen adsorbed on a promoter induces electron density transfer from the bonding
promoter to Mo changing its catalytic activity Adsorbed hydrogen induces migration of sulfur and
promoter atoms between adjacent clusters This dynamic migration causes transformation of
lsquolsquorapidrsquorsquo into lsquolsquoslowrsquorsquo sites and vice versa and therefore influences catalytic activity Migration of
Co or Ni promoter atoms to Mo sites on the rim is more likely than to Mo sites on the edge of
Co(Ni)MoS layers because the former can accept promoter atoms from both upper and lower layers
A method to evaluate the efficiency of CoMoS catalysts for HDS of various types of crudes has
been developed The proposed model provides crutial information for rational design of improved
hydrotreating catalysts and selection of preferred catalytic reaction conditions for various types of
hydrocarbon feedstock via optimization of the density and ratio of lsquolsquorapidrsquorsquo and lsquolsquoslowrsquorsquo catalyst
active sites
Application of the dynamic model to the investigation of the mechanism of the mixed alcohol
synthesis (MAS) over TMS catalysts modified by potassium gives us ground to assume that the
reaction of alcohol formation from synthesis gas proceeds on almost the same types of active sites
as it takes place for HDS Unlike HDS sites responsible for hydrogenolysis of CS bond the MAS
sites responsible for alcohol formation are modified by potassium (Fig 1)
Fig 1 TEM images of the CoMoSAl2O3 catalyst modified by 5 10 and 15 of K and the models of
intercalation of K+
ions between the layers of the MoS2 crystallites
The TEM data witness that K addition increases stacking number The catalytic examinations show
that potassium promotes alcohol yield Basing on these data we suppose that K ions intercalate
between neighbouring MoS2 layers affecting the active phase morphology and (AS)rsquos selectivity in
MAS The Co-promoted catalyst is more selective to alcohols than the non-promoted one
Promoting activity Co in MAS and HDS lets us suppose that the nature of the active sites operating
in both reactions is similar [1] VM Kogan PA Nikulshin Catal Today 149 (2010) 224
[2] VM Kogan PA Nikulshin NN Rozhdestvenskaya Fuel 100 (2012) 2
[3] VM Kogan NN Rozhdestvenskaya IK Korshevets Appl Catal A Gen 234 (2002) 207
1100 KK 1155 KK 55 KK
179
P68
RELATIONSHIP BETWEEN ACTIVE PHASE MORPHOLOGY AND
CATALYTIC PROPERTIES OF THE CARBON-ALUMINA-SUPPORTED
Co(Ni)Mo CATALYSTS IN HDS AND HYD REACTIONS
PA Nikulshin1 VA Salnikov
1 AA Mozhaev
1 PP Minaev
1 VM Kogan
2 AA Pimerzin
1
1 - Samara State Technical University Samara Russia
2 - ND Zelinsky Institute of Organic Chemistry RAS Laboratory of catalysis by trasition metals
and their compounds Moscow Russia
Effects of activated carbon of a carbon-coated alumina (CCA) support and active phase morphology
of transition metal sulfide (TMS) catalysts in hydrotreatment (HDT) of S-containing compounds
were studied The catalysts were synthesized from Anderson-type heteropolycompounds and
characterized with multiple methods X-ray powder diffraction N2 physisorption temperature-
programmed desorption of ammonia pyridine-adsorbed Fourier transform infrared spectroscopy
H2 temperature programmed reduction and high resolution transmission electron microscopy The
catalysts were tested in hydrodesulfurization (HDS) of thiophene dibenzothiophene and HDT of
diesel To interpret the obtained results we used an interlayer dynamics concept developed recently
[1] The TPR measurements indicate hydrogen uptake by the C-coated support at reaction
temperatures It witnesses that CCA accumulates gas-phase hydrogen and could be a source of
hydrogen for HDT reactions Carbon affects active phase morphology changing the carbon content
it is possible to vary a stacking numberlinear size ratio of the active phase particles and thereby to
control hydrogenation to direct desulfurization (HYDDDS) selectivity (Fig 1)
Average stacking num
ber
L
N
Average length nm12
1416
1820
2224
2628
3032
3032
3436
3840
4244
46В
06
08
10
12
14
16
18
20
22
24
26 24
18
15
06
)(s10 TOF14
SHYDDS
Average length nm Ave
rage
sta
ckin
g num
ber
L
N
12
14
16
18
20
22
24
26
28
30
32
Var130
3234
3638
4042
4446
Var2
03
04
05
06
07
08
09
Var3
07
06
05
04
03
(a) (b)
1
2
3
4
1rsquo
2rsquo
3rsquo
4rsquo
2 - 2rsquo
1 - 1rsquo4 - 4rsquo
3 - 3rsquo
(c)
Fig 1 3D dependences of TOF number (a) and HYDDDS selectivity (b) in DBT HDS on average
length and average stacking number of Co(Ni)MoS2 particles in the catalysts schematic
visualization of the morphology of promoted MoS2 slabs variation depending on the number of the
active sites on the edges and rims of the slabs (c)
An increase in the average linear size of the slab leads to a drop of HDS and HYD activities The
longer layers in the slabs the fewer solid angles are and so the higher the effect of the support On
the contrary in the multilayered structure the support effect diminishes The observed high
HYDDDS selectivity of the catalysts synthesized from AHM and nickel nitrate may be caused by
low edge surface Ni on the MoS2 slab which should also form the unpromoted Mo-sites responsible
for the HYD reactions on the edges The results suggest that the catalytic activity in HDS and HYD
reactions depends on the shape of crystallites of the active phase The results are interpreted using
recently proposed concepts of interlayer dynamics These concepts are helpful in establishing
structure-activity relations for TMS 1 VM Kogan PA Nikulshin NN Rozhdestvenskaya Fuel 100 (2012) 2
180
P69
GENESIS OF HDT CATALYSTS PREPARED WITH THE USE OF
Co2Mo10HPA AND COBALT CITRATE STUDY OF THEIR GAS AND
LIQUID PHASE SULFIDATION
PA Nikulshin1 AV Mozhaev
1 KI Maslakov
2 AA Pimerzin
1 VM Kogan
3
1 - Samara State Technical University Samara Russia
2 - MV Lomonosov Moscow State University Chemistry Department Moscow Russia
3 - ND Zelinsky Institute of Organic Chemistry RAS Laboratory of catalysis by trasition metals
and their compounds Moscow Russia
Production of clean fuels with less than 10 ppm sulfur content is one of the most important and
claiming the attention problem in recent petroleum refinery The countermeasures for the ultra deep
desulfurization are to apply novel highly active catalysts and to optimize the operation condition of
the hydrodesulfurization (HDS) process The development and application of more active and stable
catalysts could enhance the productivity and improve the product quality without negative impacts
on capital investment
Genesis of alumina supported hydrotreating (HDT) catalysts prepared with the use of
decamolybdodicobaltate heteropolyanion (Co2Mo10HPA) and cobalt citrate during their sulfidation
processes and deactivation in diesel HDT has been investigated The sulfidation stage was studied
for two procedures gas phase sulfidation by H2SH2 and liquid phase treatment by a mixture of
dimethyldisulfide in diesel at various temperatures and durations The catalysts have been studied
by N2 adsorption thermogravimetric analysis X-ray photoelectron spectroscopy and high-
resolution transmission electron microscopy methods The catalysts were tested in HDT of mixture
of 70 wt straight run gas oil with 16 wt light cycle oil and 14 wt light coker gas oil
Mechanisms of the active phase formation in the course of gas and liquid phase sulfidation
processes have been established (Fig 1)
Fig 1 CoMoS phase formation
mechanisms during gas and liquid phase
sulfidation of the Co3(CA)45-
Co2Mo10Al2O3 catalyst (S ndash average
stacking number L ndash average length
were found from TEM Co content in
CoMoS phase and (CoMo)slab were
found by XPS)
It was found that gas phase sulfidation led to formation of the CoMoS active phase with higher
cobalt content comparing to liquid sulfidation of the catalyst and initial activity of the gas phase
treated catalysts in diesel HDT was also higher than catalysts subjected to liquid sulfidation
Catalytic examination after accelerated deactivation conditions showed that the liquid phase
sulfided sample was more resistant to the deactivation Probably it is due to stabilization of active
phase particles by coke formed intensively during liquid phase sulfidation In liquid phase
sulfidation both metals are sulfided simultaneously with the formation of nuclei of CoMoS phase II
type at low temperature (2300C) At high temperature (340
0C) the increase of particle size of
CoMoS phase is occurred
181
P70
SYNTHESIS OF HEPTASACCHARIDE FRAGMENT CORRESPONDING
TO α-(1-3)-GLUCAN OF ASPERGILLUS FUMIGATUS
MV Orekhova BS Komarova NE Nifantiev
Laboratory of Glycoconjugate ChemistryND Zelinsky Institute of Organic Chemistry Russian
Academy of Sciences Leninsky Prospect 47 119991 Moscow Russia
For immunocompromised individuals Aspergillus fumigatus is the most important and life
threatening pathogen [1] In the cell walls of this ubiquitous fungus -(1rarr3)-glucan constitutes the
main polysaccharide [2] which forms biofilms and is a cause of permanent infection [3] Previously
a synthesis of spacer armed -(1rarr3)-pentaglucoside conjugates with BSA and biotin was achieved
These derivatives were used for obtaining and characterization of antibodies recognizing α-(1rarr3)-
glucan which were used for tracing A fumigatus cells However for the final goal of the project the
development of a vaccine against A fumigatus the five glucosyl units in the chain is not enough
In the present report a synthesis of 3-aminopropyl -(1rarr3)-pentaglucoside 1 (Scheme) is
described The success of convergent scheme toward the target compound relied on the use of
disaccharide 2 which was modified by orthogonal levulinoyl (Lev) and p-methoxyphenyl (pMP)
groups The ability to remove Lev and pMP groups independently made it possible to prepare
disaccharide donor 5 and acceptor 3 from one precursor and then to combine them to get
tetrasaccharide 6 Glucosylation of the trisaccharide acceptor 9 with tetrasaccharide donor 8
proceeded smoothly to give heptasaccharide backbone Stereoselectivity of each -glucosylation of
the whole scheme was controlled by -stereodirecting benzoyl group at O-6 [4] While high yields
of all glucosylations were attained due to the choice of N-phenyl-trifluoracetidoyl leaving group and
MeOTf as a promoter [5] Free heptasaccharide 1 was converted to BSA and biotin conjugates
using amino group of the spacer
1 A Gastebois C Clavaud V Aimanianda J P Latgeacute Future Microbiology 2009 4 583
2 D Maubon S Park M Tanguy M Huerre C Schmitt M C Preacutevost D S Perlin J P Latgeacute A
Beauvais Fungal Genetics and Biology 2006 43 366
3 A Beauvais C Schmidt S Guadagnini P Roux E Perret C Henry S Paris A Mallet M C Preacutevost
J P Latgeacute Cellular Microbiology 2007 9 1588
4 B S Komarova M V Orekhova Y E Tsvetkov N E Nifantiev Carbohydrate Research 2014 384
70
5 B S Komarova Y E Tsvetkov Y A Knirel U Zaumlhringer G B Pier N E Nifantiev Tetrahedron
Letters 2006 47 3583
182
P71
SUPRAMOLECULAR STRUCTURES IN ADDUCTS OF
CYMANTRENECARBOXYLIC ACID WITH FIVE- AND SIX-MEMBERED
AROMATIC N-BASES
PS Koroteev AB Ilyukhin ZhV Dobrokhotova VM Novotortsev
N S Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences
One of the goals of supramolecular chemistry is the search for new molecules that are potentially
capable of self-assembly owing to nonvalent interactions The molecule of
cyclopentadienyltricarbonylmanganese (η5-C5H5)Mn(CO)3 (cymantrene) which has the ldquopiano
stoolrdquo shape besides of many other peculiarities has specific properties as a potential building
block for supramolecular architectures both due to its special geometry and the nature of its
constituent moieties Earlier we have studied the crystal-chemical behavior of anions of
cymantrenecarboxylic acid (η5-C5H4COOH)Mn(CO)3 (HL) and more sterically hindered β-
cymantrenoylpropionic acid (η5-C5H4CO(CH2)2COOH)Mn(CO)3 combined with alkaline metals
cations and with protonated molecules of polytopic nitrogen bases which have various geometries
and provide opportunities for supramolecular interactions [1]
New derivatives of HL and polytopic aromatic N-bases imidazole (I) pyrazole (II) 3-amino-124-
triazole (III) 4-amino-124-triazole (IV) 2-aminopyridine (V) 3-aminopyridine (VI) 4-
aminopyridine (VII) 24-diamino-6-hydroxypyrymidine (VIII) were obtained and characterized by
X-ray diffraction
It has been shown that two- and three-dimensional supramolecular structures of these derivatives
are formed owing to special properties of the cymantrene moiety in particular its ability to form
COhellip
H hydrogen bonds (HBs) but the type of the structure is mostly determined by the geometry of
the cation and by its capability of HBs formation (Fig1) The possibility of organic molecules of
various nature to self-organize due to protonation andor HBs formation and with regard to specific
geometries is discussed
Fig 1 Fragments of the structures of VIImiddotHL (left) and VIIImiddotHL (right)
[1] AB Ilyukhin PS Koroteev MA Kiskin ZhV Dobrokhotova VM Novotortsev Journal of
Molecular Structure 1033 (2013) 187ndash199
Acknowledgements This study was financially supported by the RFBR (No 13-03-12428 14-03-00463) the
Council on Grants of the President of the RF (NShshy171220143) and the Presidium of the Russian
Academy of Sciences
183
P72
NUCLEOFILIC BROMO- AND IODODIFLUOROMETHYLATION OF
ALDEHYDES
MD Kosobokov VV Levin MI Struchkova AD Dilman
IOC RAS Moscow Russia
Nowadays RuppertminusPrakash reagent (Me3SiCF3)1 and its functionalized analogues
2 3 are widely
applicable fluorinated reagents in organic synthesis Indeed these air stable silanes are convenient
agents for nucleophilic fluoroalkylation reactions They exhibit their nucleophilic reactivity under
silaphilic Lewis base activation generating a pentacoordinate intermediate which could react with
a suitable electrophile (eg aldehydes) Reactions of the RuppertminusPrakash reagent (X =F) and
chloro-substituted analog (X = Cl) as well as many other functionalized silanes follow this
pathway
However reactions of a bromo-substituted silane (X = Br) with aldehydes mediated by a fluoride
ion have been unsuccessful presumably owing to facile decomposition of anionic intermediate to
difluorocarbene Indeed silane Me3SiCF2Br can generate difluorocarbene even in the presence of
weak Lewis bases such as chloride and bromide ions While (bromodifluoromethyl)trimethylsilane
(1a) can be readily obtained from the RuppertminusPrakash reagent iodinated silane (1b) has not been
known We prepared silane 1b from silane 1a in 70 yield by the brominezinc exchange followed
by iodination
Then we developed a method for nucleophilic bromo- and iododifluoromethylation of aldehydes
using bromo- and iodo-substituted difluoromethyl silicon reagents (Me3SiCF2X) The reaction is
performed in the presence of a combination of tetrabutylammonium and lithium salts Bu4NXLiX
(X = Br or I) in propionitrile4
It is believed that in this process a short-lived halodifluoromethyl carbanion serves as nucleophile
which is reversibly generated from difluorocarbene and a halide anion
This work was supported by the Russian Science Foundation (project 14-13-00034)
[1] Liu X Xu C Wang M Liu Q Chem Rev 2014 ASAP doi101021cr400473a
[2] Kosobokov M D Dilman A D Struchkova M I Belyakov P A Hu J J Org Chem
2012 77 2080minus2086
[3] Kosobokov M D Dilman A D Levin V V Struchkova M I J Org Chem 2012 77
5850minus5855
[4] Kosobokov M D Levin V V Struchkova M I Dilman A D Org Lett 2014 16 3784
184
P73
NEW REGIOSELECTIVE ROUTE TO 5-CARBOXY-123-TRIAZOLES VIA
PALLADIUM-CATALYZED CARBONYLATION OF 5-IODO-123-
TRIAZOLES
YN Kotovshchikov GV Latyshev NV Lukashev IP Beletskaya
Chemistry Department Lomonosov Moscow State University Moscow Russia
Various compounds containing 123-triazole moiety are of great importance in coordination and
supramolecular chemistry medicine polymer and materials sciences [1] In particular some 5-
carboxy-123-triazoles were shown to be kinases inhibitors as well as to exhibit antiviral and
antibacterial effects [2] So far the only synthetic route to these compounds was thermal [3+2]-
cycloaddition of organic azides to propiolic acid derivatives The main drawback of the method is
low regioselectivity Formation of two regoisomers diminishes yields of desired 5-carboxy-123-
triazoles and complicates isolation of the products Since 5-iodo-123-triazoles can be prepared
from 1-iodoalkynes and azides under Cu(I) catalysis [3] the subsequent carbonylation reaction
could became a new regioselective approach to 5-carboxy-123-triazoles
We have shown that alkoxycarbonylation of 5-iodo-123-triazoles could be performed under mild
reaction conditions with 1 atm of CO in the presence of 5 Pd(OAc)2 Various functional groups
(ester hydroxyl ketone nitro) were tolerated and a number of 5-methoxycarbonyl-123-triazoles
were obtained in good to excellent yields The transformation appeared sensitive to steric effects
and bulky substituents led to decrease in reaction rate andor yield
This work was supported by RFBR (grant 11-03-00265-а)
1 (a) M Meldal C W Tornoslashe Chem Rev 2008 108 2952 (b) J E Hein V V Fokin Chem Soc Rev
2010 39 1302
2 (a) H Cheng J Wan M-I Lin Y Liu X Lu J Liu Y Xu J Chen Z Tu Y-S E Cheng K Ding J
Med Chem 2012 55 2144 (b) G S Gadaginamath M G Bhovi Indian J Chem Sect B Org Chem
Incl Med Chem 2005 44 1068
3 J E Hein J C Tripp L B Krasnova K B Sharpless V V Fokin Angew Chem Int Ed 2009 48
8018
185
P74
A GENERAL APPROACH TO THE SYNTHESIS OF THIOPHENE-
CONTAINING ELECTRON-DONOR AND -ACCEPTOR FRAGMENTS FOR
CONJUGATED POLYMERS FOR SOLAR PHOTOVOLTAIC CELLS
IO Konstantinov1 MM Krayushkin
1 ML Keshtov
2 SA Kuklin
2 VS Kochurov
3 NA
Radychev4 AR Khokhlov
2
1 - ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
2 - AN Nesmeyanov Institute of Organoelement Compounds RAS Moscow Russia
3 - MV Lomonosov Moscow State University Physical Department Moscow Russia
4 - Carl von Ossietzky University of Oldenburg Physical Department Oldenburg Germany
The goal of this work was developing a general method for creating both electron-donor and
electron-acceptor moieties in terms of dithienylethenes to use them for preparation of new
conjugated polymers as an electroactive material for solar cells Bis(trimethylstannyl)-2-dodecyl-
benzotrithiophene monomer (1) as a donor in DndashA copolymers was synthesized for the first time
from the corresponding dithienylethene with thiophene bridge [1]
B r
R
N N
SS
C8H
1 7
B r SS
N
S
H3 1
C1 5
B r B r
S
SS
C1 2
H2 5
A r n
S S
S
C1 2
H2 5
S n S n
SS
SN
C1 7
H3 5
B r B r
SS
SN
B r B r
R1
O C1 0
H2 3
C8H
1 7
C1 0
H2 3
C8H
1 7
S
O Et
B u
1
2
P
3 R =
4
5 R 1 =
6 R 1 =
Dibromides 2-6 were synthesized also analogously from dihetarylethenes [12] and used as
monomers of the electron-acceptor nature
New narrow-band conjugated polymers of type P with a rigid alternation of donor and acceptor
units were prepared on the basis of these monomers under the Stille reaction conditions in the
presence of tetrakis(triphenylphosphine)palladium as a catalyst [34]
The thermal optical electrochemical and photovoltaic properties of the copolymers were studied
[5]
1 MM Krayushkin and MA Kalik Syntheses of Photochromic Dihetarylethenes In Katritzky
editors Advances in Heterocyclic Chemistry Vol 103 Oxford Academic Press 2011 p 1-59
2 Shirinian VZ Lonshakov DV Kachala VV Zavarzin IV Shimkin AA Lvov AG
and Krayushkin MM J Org Chem 2012 vol 77 p 8112
3 Keshtov ML Marochkin DV Kochurov VS Komarov PV Parashchuk DYu
Trukhanov VA and Khokhlov AR Vysokomol Soedin Ser B 2014 vol 56 no 1 p 1
4 Keshtov ML Toppare L Marochkin DV Kochurov VS Parashchuk DYu Trukhanov
VA and Khokhlov AR Vysokomol Soedin Ser B 2013 vol 55 no 6 p 723
5 ML Keshtov SA Kuklin VS Kochurov IO Konstantinov MM Krayushkin NA
Radychev and AR Khokhlov Doklady Chemistry 2014 Vol 454 Part 2 pp 25ndash31
186
P75
PHOTOCHEMICAL REARRANGEMENT OF CHROMONES AND
BENZOFURANS
KS Chudov1 KS Levchenko
1 VN Yarovenko
1 MM Krayushkin
1 OI Kobeleva
2 TM
Valova2 VA Barachevsky
2 EP Grebennikov
1
1 - ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
2 - Photochemistry Center Russian Academy of Sciences Moscow Russia
At present optical information recording in the existing ODs is based on thermoinduced
transformation processes of substances that change the reflection properties under the action of
light Prospects for increasing the information capacity of ODs are related to the development of
multilayered photosensitive detection media based on organic compounds that being irradiated
undergo irreversible photochemical transformations of the initial non-fluorescing compounds into
fluorescent photoproducts It has recently been shown that UV-irradiated acylchromones I that do
not manifest fluorescence are irreversible rearranged to fluorescent furano[34-b]chromenones II
Based on the latter we are developing multilayered detection media for ODs of the WORM archive
type [12]
O
O
R
O
O
R1
O
O
O
R
OR
1
R2 R
2U V
I II
R R 1 R 2 = H F G A r H e ta r
We synthesized a set of benzofurans IV with a highlighted furylpropenonic fragment and
demonstrated that they under UV-illumination also transformed into tricondensed derivatives V
that is the photorearrangement by all appearances has a common character It is worthy noted that
initial compounds IV did not possess fluorescence whereas the products V did
O
O
R2
O
R1
R1
O
O
O
H
O
R1
O
R2
O
R 1= M e B r R 2 = P h A r
III
IV
R 1= M e B rV
U VB rC H2C O R 2
The fluorescence properties of the compounds due to irreversible photochemical transformations of
chromones and benzofurans in toluene were studied The quantum yields of the photoproducts were
measured Some relationships between the fluorescence properties of the photoproducts and their
structure were revealed
A part of the compounds are characterized by a high Stokes shift and other profitable properties that
provide their practical application in photosensitive detection media with nondestructive
fluorescence reading optical information
1 VA Barachevsky OI Kobeleva TM Valova AO Ait AA Dunaev AM Gorelik MM
Krayushkin KS Levchenko VN Yarovenko VV Kyiko EP Grebennikov Opt Mem amp
Neur Networks 19 (2010) 187
2 VA Barachevsky MM Krayushkin VV Kyiko EP Grebennikov Phys Status Solidi C 8
(2011) 2841
187
P76
NEW CHROMONE-CONTAINING LIGANDS
KA Myannik1 VN Yarovenko
1 KS Levchenko
2 MM Krayushkin
1
1 - ND Zelinsky Institute of Organic Chemistry RAS Moscow Russia
2 - Central Research Technological Institute ldquoTekhnomash Moscow Russia
Chromone derivatives are of doubtless interest as bioactive compounds and elements of detecting
media for multilayer optical discs of superhigh capacity We showed the possibility to synthesize
chromone-containing ligands containing fragments of thiohydrazides of oxaminic acids 1-9
1 2 3
4 56
7 8 9
O
O NN H
SO
NH
F
O
O NN H
SO
NH
F
F
O
O NN H
SO
NH
N H 2 O
O NN H
SO
NH
F
N H 2
S
O
O NN H
SO
NH
F
C O O E t
S
O
O NN H
SO
NH
N H 2
C O O E t
O
O NN H
SO
NH
OH O
O NN H
SO
NH
F
OH
S
O
O NN H
SO
NH
N H 2
C O O E t
OH
188
P77
NEW COMPLEX STRUCTURES BASED ON OXAMINIC ACID
THIOHYDRAZIDES
MM Krayushkin VN Yarovenko IV Zavarzin
ND Zelinsky Institute of Organic Chemistry RAS Moscow Russia
It is known that among thiohydrazides there are many drugs of different action which is enhanced
in many cases in the presence of metal cations We showed a possibility to synthesize complexes
from the ligands containing fragments of oxaminic acid thiohydrazides 1-3
2 3
1
The geometric parameters of synthesized complex 1 were studied by X-ray diffraction analysis (Fig
1)
Fig 1 Fig 2
The square-planar coordination mode of nickel is attained due to two additional atoms Si with a
distance of 3407(2) Aring and Oii with a distance of 3451(4) Aring (symmetry transform i x y+1 z and i
x y-1 z ) with the formation of a distorted octahedron around the nickel atom An infinite chain is
thus formed (Fig 2)
189
P78
THREE-COMPONENT CONDENSATION OF IMINOAZOLIDINONES
WITH ALDEHYDES AND MELDRUM`S ACID SYNTHESIS AND STUDY
OF PROPERTIES OF THE IMIDAZOPYRIDINE-25-DIONES
KS Krylov AN Komogorttsev BV Lichitsky AA Dudinov MM Krayushkin
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
Multicomponent reactions are indispensable tools which are used for the construction of different
heterocyclic systems The marked advantage of such a reactions are the versatility and efficiency of
synthesis of the new organic materials The diversity of the multicomponent reactions allows to
create a broad set of compounds without using the methodology of the complicated multistage
synthesis The present work devoted to the development of our previously elaborated method based
on multicomponent reaction of the heterocyclic enamines carbonyl compounds and the Meldrum`s
acid We have proposed the versatile method of preparation of the previously unknown 7-aryl-1-
phenyl-1677-tetrahydro-4H-imidazo[45-b]pyridine-25-diones 1 based on the three component
condensation of iminoazolidines 2 aldehydes 3 and the Meldrum`s acid 4
N
NNH
O
A r
O
P h
N
NH
NH
O
P h
O O
O O
Ar C H O
Et O H
ON
+ +
2 3 4 1
The properties of the obtained imidazopyridine-25-diones 1 were investigated It is demonstrated
that compounds of type 1 undergo the acid hydrolysis with formation of previously unknown 5-
substituted 1-phenylimidazolidine-24-diones 5
N
NNH
O
A r
O
P h
A c O HN
NH
O
O
P h
NH2
OA r
1 5
References
1 B V Lichitsky R M Belyi A N Komogortsev A A Dudinov M M Krayushkin Russ
Chem Bull Int Ed 2013 62 1026-1031
190
P79
RADICAL CROSS-DEHYDROGENATIVE C-O COUPLING OF 13-
DICARBONYL COMPOUNDS WITH HYDROXYLAMINE DERIVATIVES
IB Krylov AO Terent`ev BN Shelimov GI Nikishin
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russian
Federation
Cross-dehydrogenative coupling as a rule is a reaction in which two different starting molecules
are connected by a new bond with the elimination of one hydrogen atom from each of the
molecules In the last decade these reactions have attracted great attention because they can be used
to form a new bond with almost the maximum possible atom economy and do not require additional
synthetic steps for the introduction of functional groups (Hal OTf BR2 SiR3 SnR3 ZnHal etc)
that are necessary in other approaches to the cross-coupling
The cross-dehydrogenative С-С coupling was studied in most detail the C-N C-P and C-O cross-
coupling reactions are less well developed It is difficult to achieve high selectivity in the oxidative
C-O coupling because the starting compounds are prone to side oxidation and fragmentation
reactions giving for example alcohols and carbonyl compounds
In the present work the cross-dehydrogenative СndashO coupling of β-dicarbonyl compounds with
oximes[1]
N-hydroxyimides[2]
and N-hydroxyamides[2]
was performed for the first time
The reaction proceeds in the presence of the different metal-containing oxidants KMnO4
Mn(OAc)2KMnO4 Co(OAc)2KMnO4 Mn(OAc)3bull2H2O MnO2 Mn(acac)3 Fe(ClO4)3
Cu(ClO4)2bull6H2O Cu(NO3)2bull25H2O and (NH4)2Ce(NO3)6 yields are 27ndash94 The synthesis can
be easily scaled up to gram quantities of the target products The method is applicable for a wide
variety of β-diketones and β-keto esters 2-substituted malonic esters and heteroanalogues of
β-dicarbonyl compounds 2-substituted malononitriles and cyanoacetic esters are substantially less
reactive in the cross-dehydrogenative coupling with tested hydroxylamine derivatives
Apparently the oxidant serves two functions in the cross-dehydrogenative coupling reaction the
generation of N-oxyl radicals from hydroxylamine derivatives and the one-electron oxidation of
β-dicarbonyl compounds The formation of N-oxyl radicals was confirmed by ESR spectroscopy
Acknowledgements This work was supported by the Russian foundation for Basic Research (Grant
13-03-12074)
1 I B Krylov A O Terentrsquoev V P Timofeev B N Shelimov R A Novikov V M
Merkulova G I Nikishin Iminoxyl Radical-Based Strategy for Intermolecular C-O Bond
Formation Cross-Dehydrogenative Coupling of 13-Dicarbonyl Compounds with Oximes Adv
Synth Catal 2014 356 2266ndash2280 DOI 101002adsc201400143
2 A O Terentrsquoev I B Krylov V P Timofeev Z A Starikova V M Merkulova A I
Ilovaisky G I Nikishin Oxidative C-O Cross-Coupling of 13-Dicarbonyl Compounds and
Their Heteroanalogues with N-Substituted Hydroxamic Acids and N-Hydroxyimides Adv
Synth Catal 2013 355 2375ndash2390 DOI 101002adsc201300341
191
P80
THE FIRST ENANTIOSELECTIVE ORGANOCATALYTIC REACTION IN
SUPERCRITICAL CARBON DIOXIDE ASYMMETRIC MICHAEL
ADDITION OF DIPHENYLPHOSPHITE TO α-NITROALKENES
EV Kryuchkova IV Kuchurov AG Nigmatov AS Kucherenko SG Zlotin
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky prospekt 47
119991 Moscow Russia
Recently we discovered [1] that asymmetric organocatalytic reactions can be efficiently carried out
in liquid carbon dioxide We have expected that the use of CO2 in the supercritical state (sc-CO2) as
a reaction medium may be even more promising as it is characterized by higher diffusion rates and
a unique capability of dispersing poorly soluble reagents thus enhancing the reaction scope rates
and selectivity
Herein we report that α-nitroalkenes 2 enantioselectively accept diphenylphosphite (1) in sc-CO2 in
the presence of bifunctional tertiary amines 4 and 5 (5 mol )) bearing the squaramide fragment to
afford corresponding β-nitrophosphonates 3 in high yields and with enantiomeric access of up to
94 ee [2] In this way enantiomeric β-nitrophosphonates 3 and ent-3 which are precursors of
optical antipodes of β-amino phosphonic acid derivatives that occur in nature and possess valuable
biological activities were synthesized Furthermore we disclosed a significant potential of sc-CO2
for the fractional extraction of products and recovery of precious chiral catalyst The obtained
results contribute to green chemistry as they eliminate toxic organic solvents originated from
exhausting hydrocarbon resources and facilitate separation and purification steps that usually have
the highest environmental impact in chemical processes
References
1 AG Nigmatov IV Kuchurov DE Siyutkin SG Zlotin Tetrahedron Lett 2012 53 3502
2 IV Kuchurov AG Nigmatov EV Kryuchkova AA Kostenko AS Kucherenko SG
Zlotin Green Chem 2014 16 1521
192
P81
SYNTHESIS OF NEW CLASS OF ORGANIC PEROXIDES
IODOPEROXIACETALS BY TREATMENT OF ENOLE ETHERS WITH
IODINE-HYDROPEROXIDE SYSTEM
AN Kulakova AT Zdvizhkov AO Terentev RA Novikov GI Nikishin
N D Zelinsky institute of organic chemistry Laboratory for Studies of Homolytic Reactions
Moscow Russia
Organic peroxides are very common for development of antitumor and antiparasitic drugs
However effectiveness of drugs reduces due to the mobilization of cells defense mechanisms with
respect to specific substances This problem is solved by the development of new classes of
biological compounds as well as their chemical modifications
In the present work we studied the interaction of mono-and bicyclic enol ethers with a system of I2
hydroperoxide This system allows getting number of new peroxide compounds containing an
iodine atom which makes possible further modification of the peroxide molecule
Commercially available monocyclic enole esters of 23-dihydrofuran and 34-dihydro-2H-pyran
were selected as starting materials as well as their bicyclic analogs that can be synthesized by a
known method
Firstly we studied the interaction of monocyclic enol ethers with the system I2-ButOOH (TBHP)
and I2-tetrahydropyranyl hydroperoxide (THPHP) We have proposed a method to obtain
iodoperoxide with yields up to 90 The reaction is carried out in diethyl ether at 0 deg C in the
presence of 4-fold excess hydroperoxide and an equivalent amount of iodine
Having developed iodoperoxidation method we investigated the reaction of the bicyclic enole
ethers with the I2-H2O2 system Iodoperoxides were obtained with yield of 80 The reaction was
carried under the action of iodperoxidation monocyclic enole ethers at - 40 deg C When using a more
bulky t-BuOOH were obtained addition products the peroxide to double bond not containing iodine
atom In the case of THPHP reaction did not proceed at all
In this work the methodology of synthesis of a new class of organic peroxides - vicinal
iodperoxyacetals and ketals based on mono-and bicyclic enole ethers was developed These
compounds may be useful for inventing new anticancer and antiparasitic drugs
Acknowledgements
This work was supported by the Russian Science Foundation (Grant 14-23-00150)
193
P82
APPLICATION OF AZA-COPE-MANNICH REACTION FOR HIGHLY
EFFICIENT STEROSELECTIVE SYNTHESIS OF DERIVATIVES OF (2SR
3ASR 8ASR)-3A-METHYLOCTAHYDROCYCLOHEPTA[B]PYRROL-
4(1H)-ONE
IN Myasnyanko ER Lukyanenko AV Kurkin
MV Lomonosov Moscow State University
Saturated heterocyclic compounds are much more attractive objects for the development of new
drugs compared to traditionally used in medicinal chemistry heteroaromatic compounds since they
as a rule possess better solubility pharmacokinetic properties and bioavalability [1 2] In this
regard development of efficient stereoselctive methods for the syntheis of such compounds (having
patent purity) is an important task for scientists working in drug discovery field
Earlier we developed highly efficient steroselective synthesis of cis- and trans-fused 3-substituted
octahydrocyclohepta[b]pyrrol-4(1H)-ones using aza-Cope-Mannich reaction as a key step [3 4] In
the presnt work we present simple highly efficient steroselective synthesis of 2-substituted cis-fused
octahydrocyclohepta[b]pyrrol-4(1H)-ones starting from cheap cyclohexene oxide using tandem of
aza-Cope and Mannich reactions as a key step
Amino ketones 1 were obtained as sole stereoisomers in high overall yield their structures were
confirmed by X-ray (for R = Ph and i-Pr)
This work was supported by Russian Foundation for Basic Research (projects 14-03-31685 14-03-
31709 14-03-01114)
1 Ritchie T J Macdonald S J F Young R J Pickett S D Drug Discov Today 2011 16 164-
171
2 Meanwell N A Chem Res Toxicol 2011 24 1420-1456
3 Belov D S Lukyanenko E R Kurkin A V Yurovskaya M A Tetrahedron 2011 67
9214-9218
4 Belov D S Lukyanenko E R Kurkin A V Yurovskaya M A J Org Chem 2012 77
10125-10134
194
P83
SYNTHESIS AND TRANSFORMATIONS DERIVATIVES OF AMINO ACID
CONTAINING NITROGENOUS HETEROCYCLE
DR Latypova1 VA Dokichev
1 YuV Vahitova
2
1 - Institute of Organic Chemistry Ufa SC RAS
2 - Institute of Biochemistry and Genetics Ufa SC RAS
The achievements of modern pharmacology and clinical medicine are largely determined by the
synthesis of new groups of physiologically active compounds Compounds containing amino acid
pyrrolidone and hexahydropyrimidine moieties are natural and important group of biologically
active compounds A lot of them have a variety of pharmacological effects (anti-tumor anti-
platelet anti-bacterial and anti-arrhythmic etc)
In order to develop effective regio- and stereoselective methods of synthesis of the biologically
active amino acids derivatives containing nitrogen heterocycle studied the interaction of CH-acids
(acetone benzyl acetone ethyl acetoacetate and 13-acetonedicarboxylic acid diethyl ester) with
formaldehyde primary amines and amino acids in the Mannich reaction conditions On the basis of
the synthesized 13-hexahydropyrimidines containing in the 5-position the acetyl and the ester
group 5-methyl-24-dihydro-3H-pyrazol-3-ones with amino acid moieties are obtained It has been
established that the splitting of 13- hexahydropyrimidine cycle with hydrazine hydrate which
follow with retention of configuration of the optically active centers
3-Diazopyrrolidin-2-ones that are of interest as structural fragments for production analogies of γ-
aminobutyric acid - the chief inhibitory neurotransmitter in the mammalian central nervous system
are synthesized A method of obtaining inaccessible heterocyclic compounds containing a
pyrazolo[15-c]pyrimidine moiety based on the van Alphen-Huettel rearrangement of products of
13-dipolar cycloaddition 3-diazo-4-phenylpyrrolidone with dimethyl acetylenedicarboxylate and
5-diazo-exo-3-azatricyclo[521026
]decan-4-one with quinone is proposed
Among the investigated groups of substances novel compounds that have cytotoxic properties
against both cell HEK293 and SH-SY-5Y are discovered
195
P84
METALPOLYMER NANOCATALYSTS FOR HYDROGEN-OXYGEN
MICRO-POWER ENERGY SOURCES
MV Lebedeva1 NA Yashtulov
2 NE Minina
1 KS Smirnov
2 SS Gavrin
2
1 - Lomonosov Moscow state university of fine chemical technologies Moscow Russia
2 - National research university Moscow power engineering institute Moscow Russia
Development of highly active and stable nanoelectrocatalysts for micro-power energy sources
(MPES) on the basis of fuels conversion is one of the fundamental problems of modern science and
energy The modification of solid polymer membranes (SPM) by metal nanoparticles of not only
the surface but also the volume is used to create efficient catalytically active stable and cheap
materials for energy sources of new generation The introduction of inorganic components makes it
possible to enhance the exploitation characteristics of the solid polymer membranes [1-3]
At present time the most relevant and promising energy sources are fuel cells with solid polymer
electrolyte (SPE) due to their extensive use in stationary applications and mobile electronic
equipment Electrolyte in such system is proton exchange perfluorinated polymer with ionogenic
sulfo groups (ndashSO3H) of the Nafionreg type (Du Pont) that provides unipolar conductivity on
hydrogen ions [12]
As nanostructured matrix-substrate in our work it was used the Nafion type solid polymer
membrane (SPM) with a thickness of less than 02 mm The modification by one-component and
bimetallic nanoparticles of platinum and base metal of the SPM surface and volume promotes
additional catalytic oxidation of hydrogen-containing fuels (H2 C2H5OH HCOOH CH3OH and
others) Due to introduction of nano-sized metal in the polymer matrix and application of bimetallic
systems there is an increasing of the catalytic and functional activity of metal-polymer
nanocomposites and reduced the consumption of expensive Pt and Pd catalysts [12]
The aim of the present study was to establish the influence of the metalpolymers PtNf and PdNf
synthesis parameters on the catalytic activity of platinum nanoparticles in the hydrogen oxidation
and oxygen reduction reactions
The platinum metal nanoparticles solutions were prepared by the radiation chemical reduction 60
Co
in reverse micelle solutions [12] By varying the synthesis conditions one can control the
nanoparticles size content and functional properties By means of the modern physico-chemical
research methods as electron microscopy x-ray phase analysis cyclic voltammetry it was
performed the investigation of nanoparticle and nanocomposite functional properties It was found
that when reducing the size of metal nanoparticles (less than 8 nm) catalytic activity of
metalpolymer nanocomposites (current density catalytically active surface area) increases [12]
The work was supported by RFBR (grant 13-08-12407 ofi_m2)
References
[1] Yashtulov NA Flid VR Russ Chem Bull 2013 V 62 6 Р 1332-1337
[2] Yashtulov NA Revina AA Lebedeva MV Flid VR Kinetics and catalysis 2013 V 54
3 P 336-339
[3] Limpattayanate S Hunsom M Renewable Energy 2014 V 63 5 P 205-211
196
P85
TROumlGER BASE AS A SINGLE SOURCE OF CHIRALITY IN A NEW
BIS(SALICYLALDIMINATO) CATALYST FOR RING-OPENING OF
PROPYLENE OXIDE
DA Lenev1 RG Kalinin
1 VA Kardash
1 AV Kiselyova
1 IO Konstantinov
2
1 - NIOST LLC Tomsk Kuzovlevskii trakt 2 str270
2 - Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Prospekt 47
Moscow
Recently many privileged catalysts variations of C2-symmetric Schiff base salen ligands of
Jacobsen and Katsuki modified by pendant ammonium arms with nucleophilic counterions and
corresponding cobalt catalysts have been developed[1][2][3] They have been intensively used in
the popular field of stereoregular co-polymerization of alkene oxides with carbon dioxide to yield
regular polymers ndash polyalkene carbonates such as polypropylene carbonate PPC or
polycyclohexene carbonate PCHC Stereotacticity and stereointegrity of PCHC influences its
crystallinity melting point and thermal stability which is higher in the case of stereocomplex ndash
polymeric racemate[1] Co-polymerization of (rac)-propylene oxide with CO2 yields stereogradient
racemic stereocomplex PPC with improved thermal stability and thus processability[2] The PPC
material has been commercialized and the molecular formulas of the respective catalysts have been
patented heavily[3]
Troumlger base (TB)[4] could represent valuable asset for its practical use in asymmetric catalysis In
order to rely upon TB not only as fascinating but also as privileged structure we followed an
algorithm in building a molecule with a single C2 axis for the single TB diamine and single salen
core aligning sequentially the carbon of NCN bridge the metal ion and the center of (N)CC(N)
bond of unsubstituted 12-ethylenediamine
In this preliminary report we present an approach to the synthesis of the newly designed salen
complex 1 with chirality solely due to asymmetric N atoms of enantiopure TB and we report the
preparation of the system capable of efficient catalysis of cycloaddition of propylene oxide with
CO2 to yield cyclic propylene carbonate with high TON and TOF
1
1 X-B Lu W-M Ren G-P Wu Acc Chem Res 2012 45 1721-1735 G-P Wu W-M Ren Y Luo
B Li W-Z Zhang X-B Lu J Am Chem Soc 2012 134 5682-5688
2 K Nakano S Hashimoto M Nakamura T Kamada K Nozaki Angew Chem Int Ed 2011 4868-
4871 B Y Lee A Cyriac Nature Chem 2011 3 505-507
3 A Tullo Capturing Carbon in Chem Eng News June 23 2008 vol 86(25) p21 Novomer Inc WO
2011163133 2011 (S D Allen A E Cherian C A Simoneau J J Farmer)
4 F Voumlgtle Fascinating molecules in Organic Chemistry Wiley Chichester UK 1992 B Dolenskyacute M
Havliacutek VKraacutel Chem Soc Rev 2012 41 3839-3858
197
P86
GEMINAL SILICONZINC REAGENT AS AN EQUIVALENT OF
DIFLUOROMETHYLENE BIS-ANION
VV Levin AA Zemtsov MD Kosobokov AD Dilman
IOC RAS lab8 Moscow Russia
Elaboration of new methods for the synthesis of fluoroorganic compounds is important owing to
unique effect of fluorine atoms on their biological activity Synthetic methods based on the
introduction of fluorinated fragments into organic substrate are most widely presented While
various methods for the introduction of the CF3-group have been documented approaches for the
synthesis of compounds bearing CF2-fragment notably less abundant At the same time this
fragment is isosteric to ethereal oxygen which makes compounds with this moiety highly attractive
as promising pharmaceuticals Typically Synthesis of CF2-containing products involves
deoxofluorination reaction or relies on building block approach Also we recently described a
strategy for assembling these compounds from difluorocarbene nucleophile and electrophile1
We present a germinal siliconzinc binucleophilic reagent (1) for coupling with two electrophilic
spesies2 This reagent conveniently prepared by cobalt-catalyzed brominezinc exchange in
Me3SiCF2Br using isopropylzinc iodide
Under the copper catalysis reagent 1 smoothly reacts with allylic halides with formation of
fluorinated silanes 2 This silanes were employed as nucleophilic reagents with a range of
aldehydes provides after work-up the fluorinated alcohols 3 In this products both nucleophilic sites
of initial reagent 1 successively replaced by two electrophiles
Acknowledgements This work was supported by the Ministry of Sience (project MD-
475020133) Russian Foundation tor Basic Reseach (projects 13-03-12074 14-03-00293 14-03-
31253_mol_a 14-03-31265_mol_a)
[1] Levin VV Zemtsov AA Struchkova M I Dilman AD Org Lett 2013 15 917ndash919
[2] Kosobokov M D Levin VV Zemtsov AA Struchkova M I Korlyukov A A
Arkhipov D E Dilman AD Org Lett 2014 16 1438ndash1441
198
P87
THERMAL AND ALUMINUM OXIDE INDUCED GAS-PHASE RING-
OPENING TRANSFORMATION OF GEM-DIFLUORO- AND GEM-
FLUOROCHLOROCYCLOPROPANES WITH FORMATION OF 2-
FLUORO- OR 2-CHLOROBUTA-13-DIENES
NV Volchkov MB Lipkind MA Novikov OM Nefedov
ND Zelinsky Institute of Organic chemistry of Russian Academy of Sciences Leninsky prospect
47 119991 MoscowRussian Federation
It was found that gem-fluorochlorocyclopropanes 1a-d are converted into corresponding 2-
fluorobuta-13-dienes 3а-d under gas-phase pyrolysis in flow tube-reactor at 400-450degС as result of
thermal cyclopropyl-allylic ring opening transformation and dehydrochlorination Under analogous
conditions gem-difluorocyclopropanes 2a-d undergo only thermal fragmentation with elimination
of difluorocarbene to give alkenes
F F
R
R1
R2
C H 3
1 7 0 -2 5 0 degC
A l2O 3
C l
R2
R
R1
F C l
R
R1
R2
C H 3
1 a -d 3 a -d (3 5 -7 5 )
1 7 0 -2 5 0 deg C
R = R1 = H R
2 = C H 3 (a ) R
1 = R
2 = H R = C H 3 (b )
R = R2 = H R
1 = C H 3 (c ) R = R
1 = H R
2 = C l (d )
A l2O 3 F
R2
R
R1
flo w flo w
4 0 0 -4 5 0 deg C
4 0 0 -4 5 0 deg CR
R1
R2
C H 3flo w
flo w
2 a -d
4 a -d (4 5 -6 5 )
C F 2+
The character of thermal transformation of 1a-d and 2a-d is changed if the pyrolysis carry out in the
presence of Al2O3 In this case gem-difluorocyclopropanes 2a-d can be converted into 2-fluorobuta-
13-dienes 3а-d at 170-250degС as result Al2O3 promoted breaking of very strength carbone-fluorine
bond that induce cyclopropyl-allylic transformation and dehydrofluorination The ability of Al2O3
to activate the breaking С-F-bond cause also the promotion and the alteration of selectivity for ring-
opening transformation of gem-fluorochlorocyclopropanes 1a-d In contraste to homogeneous
pyrolysis heterogeneous thermolysis of 1a-d in the presence of Al2O3 at 170-250degС gave 2-
chlorobuta-13-dienes 4а-d
199
P88
AN IMPROVEMENT OF THE CATALYTIC PERFORMANCE IN THE
ASYMMETRIC MICHAEL REACTION OF PRIMARY AMINE TAGGED
TO AN N-(CARBOXYALKYL)IMIDAZOLIUM CATION
VG Lisnyak AS Kucherenko SG Zlotin
IOC RAS Laboratory 11 Moscow Russia
A (1S2S)-12-diphenylethane-12-diamine derivative modified with an N-(4-
carboxybutyl)imidazolium cation and PF6ndash anion has been developed and applied as a recyclable
organocatalyst of the asymmetric 14-conjugate addition of 4-hydroxy-2H-chromen-2-one to 1-
substituted buten-3-ones or cyclohexen-3-one to afford corresponding Michael adducts in high
yields (up to 97 ) and enantioselectivities (up to 90 ee) [1]
The most active (S)-enantiomer of
the clinically useful anticoagulant warfarin was prepared in this way The catalyst exhibited better
recyclability than its known analog [2]
which does not contain a carboxy group it could be recycled
5 times in the reaction without a significant decrease in product yield or ee values Gradual
deactivation of the catalyst was caused by leaching during workup rather than by off-cycle reactions
between the catalyst and reagents
The work was financially supported by the Russian Foundation of Basic Research (project 12-03-
00420)
[1] A S Kucherenko V G Lisnyak A O Chizhov S G Zlotin Eur J Org Chem 2014 3808
[2] A S Kucherenko D E Siyutkin A G Nigmatov A O Chizhov S G Zlotin Adv Synth
Catal 2012 354 3078
200
P89
SYNTHESIS AND SPECTRAL FEATURES OF NOVEL PHOTOCHROMIC
DIARYLETHENES OF AZOLE SERIES
AG Lvov1 EYu Bulich
2 AM Yanina
2 AM Kavun
3 VZ Shirinian
1 MM Krayushkin
1
1 - ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
2 - DI Mendeleev University of Chemical Technology of Russia Moscow Russia
3 - Higher Chemical College DI Mendeleev University of Chemical Technology of Russia
Moscow Russia
Diarylethenes with heterocyclic aromatic moieties are widely studied to develop different
electronics devices such as optical memory and molecular switches [1] To develop new
photochromic systems with improved spectral properties we have proposed a new type of the
photochromic diarylcycloalkenones of azole series Various novel photochromic diarylethenes
bearing cyclopentenone or cyclohexenone rings as ethene bridge and azole residues (oxazole
imidazole pyrazole and thiazole derivatives) as aryl moieties have been synthesized Ketoesters 1
are the key compounds in these syntheses which were prepared from commercially available
reagents in two stages To introduce diverse functional groups in ethene bridge and aryl moieties
the various synthetic methods (C-alkylation Nazarov Michael and Knoevenagel reactions) have
been used
Ar1
Ar2
O
Ar1
Ar2
O Ar3
O
Ar1
Ar2
P h
O
N
M e A r N
N
M e A r
R
N
NM e
P h
N
S
M e P h
SM e M e
Ar2
O
B r
H Ar2
O
Ar2
O
P h
Ar1
O
C O2Et
H Ar3
O
A r1 2 3 =
1
1
1
A lky la tio n + K n o e ve n a g e l co n d e n sa tio n
K n o e ve n a g e l co n d e n sa tio n + N a za ro v cyc liza tio n
M ich a e l a d d it io n + K n o e ve n a g e l co n d e n sa tio n (o n e -p o t)
2
3
4
1
1 2
The spectral characteristics of the obtained photochromic compounds as well as some features of
their preparation methods will be also discussed
Acknowledgments
This work was financial supported by Russian Foundation for Basic Research (Grant 14-03-31871)
References
[1] M Irie Chem Rev 2000 100 1685
201
P90
NEW PHOTOINDUCED REARRANGEMENT OF DIARYLETHENES
AG Lvov1 AM Kavun
2 VZ Shirinian
1 VV Kachala
1 MM Krayushkin
1
1 - ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
2 - Higher Chemical College DI Mendeleev University of Chemical Technology of Russia
Moscow Russia
Diarylethenes (stilbenes) are one of the most reactive systems in photochemistry Their cistrans
isomerization [2+2] cycloaddition and photocyclization reactions are widely known Among them
the photocyclization of diarylethenes is a subject of long standing interest This process proceeds in
accordance with the Woodward-Hoffmann rule by conrotatory 6π-electrocyclization mechanism of
the cis-form of stilbenes I leading to the formation of the thermodynamically less stable isomer
4a4b-dihydrophenanthrene II which is used in different transformations depending upon the
structure nature and on the reaction conditions including photochromic switching and the synthesis
of polyarenes
X X
R3
R4
R1
R2
X X
R3
R4
R1
R2
I I
X C H = C H O N S
h
I
N e w p ro d u c ts
h
In a continuation of our studies on the photochromic properties of diarylethenes we have found a
new skeletal rearrangement resulting in the formation of polycyclic aromatic systems [1] It was
found that the photoreaction of 12-diarylethenes 1 comprising oxazole and phenyl rings under UV
light yields to amido-substituted polyarenes 3 with high efficiency
O
N
M e A r
H
O
N
M e A r
H
H
N
M e
O
A r
h (3 6 5 n m )
3 (4 5 -8 0 )1 2
C H C l3 0 1 M
The synthetic features and possible mechanism of the new photorearrangement will be discussed
Acknowledgments
This work was financial supported by Russian Foundation for Basic Research (Grant 14-03-31871)
References
[1] A G Lvov V Z Shirinian V V Kachala A M Kavun I V Zavarzin M M Krayushkin
Org Lett 2014 accepted
202
P91
FRIEDEL-CRAFTS ALKYLATION OF FURANS WITH BENZYL
ALCOHOLS CATALYZED BY COPPER(II) SALTS
AS Makarov MG Uchuskin AV Butin
Perm State University Department of Chemistry Perm Russia
Friedel-Crafts reaction is known to be one of the most powerful tool for introduction of variety of
alkyl groups into furan ring however the use of strong Bronsted acids or hard Lewis acids leads
often to partial destruction of furan substrates due to their acidophobic nature Nevetheless
utilization of π-activated alcohols under mild catalytic conditions allows for products to be isolated
in reasonable yields [1] Various expensive Lewis acids are usually used for activation of alcohols
[2 3] Although several benzyl-substituted furans were synthesized by these procedures in
moderate to excellent yields the substrate scope has not been explored adequately Thus the
development of a general catalytic procedure for alkylation of furans with benzyl alcohols
employing inexpensive catalysts remains an important challenge
Recently we reported a copper vitriol-catalyzed domino-reaction of o-aminobenzyl alcohols with
different furfurylamines which provides a simple route to 2-acylvinyl-substituted indoles [4] Our
continuing interest in C-C bond forming reactions led us to examine other copper(II) salts in the
alkylation step We found that some copper(II) salts might be used as catalysts for the alkylation of
furans 2 with substituted benzyl alcohols 1 Resulting benzyl furans 3 were isolated in good to
excellent yields under optimized reaction conditions
O H
R1
R2
OR
3
R1
O
R3
R2
C u II
R 1 = H A lk A lk O H a l
R 2 = A lk A r
R 3 = A lk A r
+
1 2 3
Herein we report a novel copper(II)-catalyzed Friedel-Crafts alkylation protocol allowing for
synthesis of a large variety of substituted benzylfurans
We thank Russian Foundation for Basic Research (RFBR grant 14-03-31278) and Ministry of
Education and Science of Russian Federation (42462014K) for the financial support
1 M Bandini M Tragni Org Biomol Chem 2009 7 p 1501
2 S Roy S Podder J Choudhury J Chem Sci2008 120 p 429
3 M Noji et al Synthesis 2008 23 p 3835
4 Uchuskin M G Molodtsova N V Lysenko S A Strelnikov V N Trushkov I V Butin A V
Eur J Org Chem 2014 p 2508
203
P92
CATALYTIC CROSS CYCLOMAGNESIATION OF 12-DIENES IN THE
SYNTHESIS OF ZZ-DIENOIC ALCOHOLS AND 5Z9Z-DIENOIC ACIDS
VA Dyakonov AA Makarov EKh Makarova UM Dzhemilev
Institute of Petrochemistry and Catalysis Russian Academy of Sciences Laboratory Catalytic
Synthesys Ufa Russia
Intermolecular cross cyclomagnesiation of terminal aliphatic 1 and oxygenated 12-dienes 2 was
performed for the first time by means of Grignard reagents and Cp2TiCl2 to give after acid
hydrolysis of the reaction mixture oxygenated hydrocarbons containing a 1Z5Z-diene moiety 4 in
the molecule in up to 94 yields
The developed reaction formed the basis for elaboration of a new effective method for the synthesis
of 5Z9Z-dienoic acids in view of the published data concerning a broad range of biological
activities of these compounds including antimalarial antimicrobial antitumor and antiviral
activities Along with low toxicity of С20-С30 acids this makes these compounds fairly attractive
as a base for development of modern medical drugs
We suggested that the developed approach to the synthesis of oxygenated dienes by means of cross
cyclomagnesiation could serve as the basis for a new approach to the synthesis of 5Z9Z-dienoic
acids
Thus according to the scheme we proposed the first step is Cp2TiCl2-catalyzed cross
cyclomagnesiation of terminal aliphatic allenes 6 with the tetrahydropyran ether of hepta-56-dien-
1-ol 5 by EtMgBr under conditions developed above The subsequent hydrolysis of the reaction
mixture results in oxygenated dienes 7 The removal of pyranyl protection and oxidation of the
5Z9Z-diene alcohols 8 thus formed leads to target 5Z9Z-dienoic acids 9 in 45-48 yields and 98
stereoselectivity
This work was performed under financial support from the Russian Science Fondation (Grant 14-
13-00263)
204
P93
CYCLOALUMINATION OF ALKENES AND ALKYNES IN THE
SYNTHESIS OF PHOSPHOLANES AND PHOSPHOLENES
AL Makhamatkhanova VA Dyakonov RA Agliullina UM Dzhemilev
Institute of Petrochemistry and Catalysis of RAS Laboratory of catalytic synthesis Ufa Russia
Aluminacyclopentanes 1 and aluminacyclopentenes 2 generated in situ from the cycloalumination
reaction of olefins and acetylenes with Et3Al catalyzed by 5 mol Cp2ZrCl2 (toluene ~ 20 оС 12
h) were found to undergo the phenyl dichlorophosphine-mediated exchange reaction between
aluminum and phosphorus giving rise to practically important 3-alkyl(phenyl)-substituted 1-phenyl
phospholanes 3 and 23-dialkyl-substituted 1-phenyl 2-phospholenes 4 in high yields after
hydrolysis of the reaction mixture The resultant phosphanes 3 and 4 corresponding readily form
oxides and sulfides on treatment with hydrogen peroxide in chloroform or elemental sulfur
The structure of the synthesized compounds has been established by one- (1H
13C Dept 135) and
two-dimensional (HSQC HMBC и HH COSY) NMR techniques The effect of the reagent ratio
duration and temperature of the reaction on the yield of the desired phosphacarbocycles is
discussed
This work was supported financially by the Russian Foundation for Basic Research (Grants 12-03-
31259 14-03-31084) and NSh-213620143
1 UM Dzhemilev AG Ibragimov AP Zolotarev RR Muslukhov and GA Tolstikov Bull
Acad Sci USSR Div Chem Sci 1989 38 194
2 VA Drsquoyakonov Dzhemilev Reactions in Organic and Organometallic Synthesis NOVA Sci
Publ New-York 2010 96 p
3 UM Dzhemilev Mendeleev Commun 2008 18 1
205
P94
PIONEERING IONIC LIQUID-PROMOTED NUCLEOPHILIC AROMATIC
CINE-SUBSTITUTION OF HYDROGEN
NN Makhova MA Epishina AS Kulikov
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Rissia
The nucleophilic substitution of hydrogen in electron-deficient arenes (SNH) is a general process of
great practical value1 Over the past decades several variants of SN
H processes were opened and
investigated in details the oxidative nucleophilic substitution of hydrogen the vicarious
nucleophilic substitution (VNS) the cine- and tele-substitution the ANRORC substitution The
cine-substitution is a process in the course of which the entering nucleophilic group takes up a
position adjacent to that occupied by the leaving group One of the cine-substitution example is
conversion of substituted nitrobenzenes into benzoic acids under the action of KCN excess in
aqueous EtOH (the von Richter reaction) The carboxylic group always enters in orto-position to
leaving nitro group This transformation occurs by heating of different substituted nitrobenzenes in
the presence of the KCN excess in refluxing 48 aqueous ethanol during 48-50 h or in a sealed
tube at 150-180 oC during 1-2 h Yields of final benzoic acids were as a rule low or the expected
benzoic acids were not generated at all In addition the reaction is accompanied by a large amount
of acidic tar apparently polymeric by nature
In this work we have found that transformation of electron-deficient arenes (nitrobenzene 1a and 4-
Cl- (1b) 4-Br- (1c) 4-F- (1d) 4-I- (1e) and 4-MeO- (1f) nitrobenzenes) to corresponding benzoic
acids 2a-f under the action of the KCN excess in aqueous EtOH (von Richter reaction) was
promoted by ionic liquids (ILs) Our research team has great expertise and successful experience in
the performance of various reactions in Ils2
Screening of the conditions for the synthesis of m-
chlorobenzoic acid 2b from of 4- chloronitrobenzene 1b shown that the optimum molar ratio ionic
liquid [bmim]BF41b is 1751 or 175 mol of [bmim]BF4 All tested cases of the von Richter
reaction of nitroarenes 1a-f in the presence of ionic liquids proved successful and produced those
results which were not possible in before described conditions The influence of nature of the
substituents in nitrobenzenes on the reaction results was revealed ndash the stronger electron-donating
properties of substituents the slower the reaction This finding is the first case of the nucleophilic
aromatic cine-substitution of hydrogen promoted by ionic liquids
1 F Terrier Modern Nucleophilic Aromatic Substitution Wiley-VCH Weinheim 2013 488 pp
2 N N Makhova M I Pleshchev M A Epishina AS Kulikov ldquoSynthesis and transformation
of nitrogen-containing heterocycles in iionic liquidsrdquo Khim Heterocycl Soedin 2014 (5) 690-
703 (in Russian)
This work was supported by Russian Foundation for basic Research (grant 13-03-00153a)
206
P95
REACTIONS OF ADDITION OF THIOPHENOL TO PROPARGYL
SYSTEMS AND BIOCHEMICAL ACTIVITY OF OBTAINED COMPOUNDS
VM Farzaliyev PSh Mammadova ER Babayev HSh Aliyeva IM Eyvazova
AMGuliyev Institute of Chemistry of Additives of Azerbaijan National Academy of Sciences
(ANAS) Beyuk-Shor Str Block 2062 AZ1029 Baku Azerbaijan
High reactivity of thiols allows to easily conduct thiylling of multiple carbon-carbon bonds These
reactions are convenient methods of synthesis of the various derivatives possessing practically
interesting properties and also they can be considered as modelling ones for some physiologically
important processes occurring in live organisms
The research of reactions of nucleophylic radical and non-catalytic addition of aromatic tiols to
acetylene alcohols with account of structure properties of initial reagents gives an opportunity to
establish theoretic bases at purposeful synthesis of practically interesting compounds
We synthesized phenyl thioalkenols at the condition of nucleophylic radical and non-catalytic
addition and carried out comparative analysis of results obtained for all three types of reactions
taking into account structure of initial acetylene alcohols (propargyl methyl - dimethyl- and
methylethylethynilcarbinols) and thiophenol The basic parameters such as molar rate of initial
reagents duration and temperature for these reactions remained to be unchanged
Isomer content and rate of cis- trans-conformers were established by H1 NMR-spectra
Identification of α and β- isomers was carried out on resonance signals of =CH2- and CH=CH-
groups but rate of cis- trans-conformers was determined by analysis of results of integration with
account of constant of spin-spin interaction H1
NМR-research of reactionary mixture was carried
out till its separation to exclude the influence of isomer processes as far as possible Part of β-
isomer (cis- + trans-) was used as quality measure of influence of factors of initial reagents structure
on regioselectivity Under these conditions the part of cis- trans-conformers was the measure of
influence on stereo specificity
Composition structure and yield of products of reaction of nucleophylic radical and non-catalytic
addition of thiophenol to propargyl systems are determined by electronic (to a lesser degree) and
steric factors of the structure of the reacting compounds mainly acetylene ones The direction of
the attack (regiodirectivity) is controlled by space difficulties formed by both reagents at their
direct interaction but stereoselectivity depends on the steric factors of the structure mainly thiol
compounds
It has been shown that reaction of non-catalytic addition of arylthiols to propargyl systems is a
convenient and technologically accessible method for purposeful synthesis of arylthio - and
cyclohexylthioamines with high yields The reaction proceeds basically on nucleophylic
mechanism and with partial participation of thiyl radicals
There has been revealed high antimicrobial effectiveness of series of the synthesized sulphides in
lubricating oils fuels and cutting liquids
207
P96
AN EXPERIMENTAL APPROACH FOR THE ESTIMATION OF CRYSTAL
LATTICE ENERGY OF CO-CRYSTAL
AN Manin AP Voronin GL Perlovich
GA Krestov Institute of solution chemistry of the Russian academy of scienses Physical
Chemistry of Drugs department Ivanovo Russia
The creation of pharmaceutical co-crystals is an area of expanding growth These materials offer a
possible route for the modification of the physicochemical properties of APIs such as solubility
physical and mechanical properties thermodynamic stability etc without changing the
pharmacological activity The key design tool used to select a suitable compound (a co-crystal
former) for a given substance is the concept of supramolecular synthon [1] Several types of
supramolecular synthon are usually realized in two-component crystals and are characterized by
intermolecular hydrogen bonds (H-bonds) of different types and strengths The energy of these
interactions was evaluated in a number of papers [2] A lot less attention has been paid to the
quantitative description of the intermolecular interactions of homo- and heterodimers with the
neighbor molecules which play an important role in the successful co-crystal phase formation The
cumulative characteristic of the intermolecular (noncovalent) interactions in solids is the
sublimation enthalpy ΔHsub This value extrapolated to 0 K corresponds to the crystal lattice energy
Elatt Despite the active investigation of various physicochemical properties of co-crystals no papers
concerning co-crystal sublimation have been published until now
The aim of our study is to provide an experimental validation of the transpiration method for co-
crystal enthalpy of sublimation estimation The present research work considers the co-crystal of 2-
hydroxybenzamide (salicylamide A) with 4-acetamidobenzoic acid (acetamidobenzoic acid B)
This co-crystal is chosen for the following reasons (i) The acidminusamide heterosynthon is a persistent
H-bond motif in co-crystal structures (ii) Salicylamide is an active pharmaceutical ingredient while
acetamidobenzoic acid is safe for human consumption (iii) The thermodynamic functions of
sublimation for both components have been obtained by us earlier
A novel 11 co-crystal of salicylamide and 4-acetamidobenzoic acid was obtained by DSC
screening procedure as well as grinding (both neat and solvent-drop) and solvent evaporation
techniques A complete thermal analysis performed by DSC TG and hot stage microscopy
revealed that the co-crystal remains stable in its solid form until the melting point at 1824 degC
where it breaks down into components To determine the optimal conditions of single crystal
growth a triangle phase diagram for the object system with ethanol was built An X-ray diffraction
experiment with complete solving of the crystal structure was carried out for the co-crystal For the
first time in literature the sublimation thermodynamics of a multicomponent crystal was studied
experimentally by the transpiration method in a quasi-equilibrium mode A presumable mechanism
of the sublimation process was proposed with the heterodimer sublimating and eventually
dissipating into separate molecules
1 Desiraju G R Crystal Engineering From Molecule to Crystal J Am Chem Soc 2013 135
27 9952minus9967
2 Dunitz J D Gavezzotti A Supramolecular Synthons Validation and Ranking of
Intermolecular Interaction Energies Cryst Growth Des 2012 12 5873minus5877
This work was supported by the Russian Scientific Foundation (14-13-00640) We thank ldquothe
Upper Volga Region Centre of Physicochemical Researchrdquo for technical assistance with DSC and
XRPD experiments
208
P97
SELECTIVE C-H ALKENYLATION OF ARYL ETHERS AND
THIOETHERS IN MIXTURES
AN Marjanov1 KV Luzyanin
1 VP Ananikov
2
1 - Laboratory of Cluster Catalysis Saint Petersburg State University Universitetsky pr 26 Stary
Petergof 198504 Russia
2 - Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Prospekt 47
Moscow 119991 Russia
Direct CndashH alkenylation of arenes assisted by the directing group represent one of the most atom-
economic approaches for the preparation of 12-disubstituted olefines1ndash5
While the alkenylation of
single starting material is a well-established strategy the selective alkenylation of a sole component
in a mixture of substrates is not known
S
N
2-(phenylthio)pyridine
S
N
2-(phenylsulfinyl)pyridine
O
O
N
2-phenoxypyridine benzyl(phenyl)sulfane
S
A B
Y
X
CO2Et
oxidant catalystsolvent D
Y
X
CO2Etmixtures of three or four substrates
single product
Scheme 1 Substrates used for this study (A) and a selective CH alkenylation of a mixture of
substrates with ethyl acrylate (B)
In pursuit of our studies we discovered that careful optimization of reaction conditions for CndashH
alkenylation eg solvent oxidant catalyst reaction temperature and ratio of substrates turns out
possible a selective alkenylation of a single component in a mixture of substrates Indeed several
different mixtures of aromatic ethers and thioethers were studied toward ethyl acrylate as
alkenylating source (Scheme 1) For each mixture only a sole component was a subject of
alkenylation while all others remained intact
In the current report we summarize obtained data regarding CndashH alkenylation of mixtures of ethers
and thioethers making a particular emphasis on improving the selectivity of the process and
understanding its driving forces
Acknowledgements This work has been partially supported by the Saint Petersburg State
University (research grant from Laboratory of Cluster Catalysis) and the Russian Fund for Basic
Research (grant 14-03-01005)
[1] Garciacutea-Rubia A Fernaacutendez-Ibaacutenez M A Goacutemez Arrayaacutes R Carretero J C Chem Eur J
2011 17 3567ndash3570 [2] Yu M Xie Y Xie C Zhang Y Org Lett 2012 14 2164ndash2167 [3]
Zhang X-S Zhu Q-L Zhang Y-F Li Y-B Shi Z-J Chem Eur J 2013 19 11898ndash11903
[4] Shi B-F Zhang Y-H Lam J K Wang D-H Yu J-Q J Am Chem Soc 2010 132 460ndash
461 [5] Liu B Jiang H-Z Shi B-F J Org Chem 2014 79 1521ndash1526
209
P98
SYNTHESIS AND CHARACTERIZATION OF DENDRIMERS DERIVED
FROM GLYCEROL
B Menot J Stopinski S Bouquillon
Institut de Chimie Moleculaire de Reims CNRS UMR 7312 Universite de Reims Champagne
Ardenne ndash UFR Sciences Exactes et Naturelles BP 1039 51687 Reims Cedex 2 France
For several years the laboratory was interested in the development of dendrimers using various
organic biosourced by-products the valuation of which being a real interest for our region One of
the first explored strategies was based on the decoration of nitrogen-based dendrimers
(commercially available polypropyleneimines (PPIs)) [1] with by-products of glycerin The toxicity
of these decorated nitrogenous-based dendrimers was evaluated [2] and their potential in catalysis
or in encapsulation demonstrated [13]
The synthetic strategy envisaged now by our team is to apply our decoration strategy to
commercially available polyamidoamines (PAMAMs) and to synthesize directly from the glycerin
new families of dendrimers The preparation of these last dendrimers directly from biobased
building blocks should improve their biodegradation and decrease their toxicity what is essential
for environmental applications
The objective of this presentation is to present our preliminary results concerning the development
of these new glycerodendrimers [4]
[1] S Balieu A El Zein R De Soussa F Jeacuterocircme A Tatiboueumlt S Gatard Y Pouilloux J
Barrault P Rollin S Bouquillon Adv Synth Catal 2010 352 1826
[2] S Balieu C Cadiou A Martinez J-M Nuzillard J-B Oudart F-X Maquart F Chuburu S
Bouquillon J Biomed Mater Res Part A 2013 101A (3) 613-621
[3] K Fhayli S Gatard A Mohamadou L Dupont S Bouquillon Inorg Chem Comm 2013
27 101
[4] B Menot J Stopinski A Martinez S Bouquillon publication in preparation
210
P99
PALLADIUM-CATALYZED HIGHLY REGIOSELECTIVE
PHOSPHONATION OF MESO-UNSUBSTITUTED PORPHYRINS VIA
C(sp2)-H FUNCTIONALIZATION
EA Mikhalitsyna ES Podyacheva IP Beletskaya
MSU Faculty of Chemistry Moscow Russia
Synthesis of new artificially modified porphyrins has received much attention as a very attractive
and promising goal for catalysis medicine light-absorbing materials mimicking the antenna
complexes of photosynthetic system photovoltaics etc1 In our work we are focused on the
development and optimization of high regioselective C-H phosphonation of porphyrins and their
metal complexes in meso-position via oxidative Pd(II)-catalyzed dehydrogenative cross-coupling
(CDC) Surprisingly to the best of our knowledge there are very few catalytic examples regarding
the C(sp2)ndashP bond formation through direct phosphonation of the CndashH bond with phosphite ester
including a limited class of compounds with acid C-H bond such as coumarins azoles terminal
alkynes and α‑ amino ketones2-5
We herein report the first example of the catalytically oxidative
phosphonation of meso-unsubstituted porphyrins which has attracted great attention for excellent
atom economy and an enviromentally friendly approach in opposite to classical tremendous
multistep synthesis6
To study the influence of structural factors on the reactivity of porphyrin substrates the target series
of meso- tris- di- and mono-mesityl substituted porphyrins and their Ni(II) and Zn(II) metal
complexes were synthesized by condensation of corresponding dipyrrylmethanes with
mesitylaldehyde in the presence of an acid catalysts and oxidant7 Pd(II)-catalyzed C-H
posphonation of Ni(II) 5-mesitylporphyrin (NiPMes) was successfully carried out with 40 mol
Pd(OAc)2 as catalyst 12 eq of 44rsquo-bipyridine as ligand 6 eq of K2S2O8 as oxidant and excess of
diethyl phosphite in refluxed dioxane under air atmosphere during 24 hours (Fig 1) Target mono-
phosphotated product were obtained and separated by column chromatography in good 80 yield
along with 14 of bis-phosphonated product The same conditions were used for phosphorylation
of bis-510-dimesityl and tris-51015-trimesitylporphyrins to prepare in 42 and 29 mono- and
diphosphonated porphyrins correspondingly
Fig 1 Pd-catalyzed C-H phosphonation of 5-mesitylporphyrin
1 J Mack Z Shen N Kobayashi In Handbook of Porphyrin Science Kadish K M Smith K M Guilard R Eds
World Scientific Publishing Singapore 2012 Vol 23 pp 281minus373
2 X Mi M Huang J Zhang Ch Wang and Y Wu Organic Letters 2013 15 pp 6266ndash6269
3 Ch Hou Yu Ren R Lang X Hu Ch Xia and F Li Chem Commun 2012 48 pp 5181ndash5183
4 Y Gao G Wang L Chen P Xu Y Zhao Y Zhou and L-B Han J Am Chem Soc 2009 131 7956-7957
5 B Yang T-T Yang X-A Li J-J Wang and S-D Yang Org Lett 2013 15 19 5024ndash5027
6 Yu Y Enakieva A G Bessmertnykh Yu G Gorbunova Ch Stern Y Rousselin A Y Tsivadze and R Guilard
Organic Letters 2009 17 pp 3842-3845
7 Ch Bruumlckner J J Posakony C K Johnson R W Boyle B R James and D Dolphin J Porphyrins
Phthalocyanines 1998 2 pp 455ndash465
211
P100
SYNTHESIS AND REACTIVITY OF 7-AMINO-4-OXO-3-R-8-Rrsquo-6H-
PYRAZOLO[51-C][124]TRIAZINES
LM Mironovich DV Shcherbinin AY Podolnikova
Southwest State University Basic Chemistry and Chemical Technology Kursk Russia
Reactivity of the 124-triazine derivatives containing pyrazole ring in the structure is now
intensively studied 7-Amino-4-oxo-3-R-8-Rrsquo-6H-pyrazolo[51-c][124]triazines (23) has been
synthesised by refluxing compound (1) with malononitrile and ethyl cyanoacetate in the medium
pyridine [1]
Boiling of compound (2) with KOH in the alcoholic medium has led to hydrolysis with isolation of
compound (4) it was treated with HCl and received pyrazolo[51-c][124]triazine-8-carboxylic acid
(5) Decarboxylation at high temperatures leads to isolation of compound (6) Pyrazolo[51-
c][124]triazine-8-carbohydrazide (7) obtained by boiling compound (2) with N2H4 in the alcoholic
medium
Refluxing of compound (3) in the alkaline medium has led to carbamide (8)
Boiling of compound (8) with formic acid has led to pyrimido[4rsquo5rsquo34]pyrazolo[51-
c][124]triazines (10) The structure of compound (10) was determined by X-ray crystallography
For fant of reflux P2S5 in pyridine with compound (10) leads to 411-dithioxo-3-R-6H10H-
pyrimido[4rsquo5rsquo34]pyrazolo[51-c][124]triazine (11) and 11-oxo-4-thioxo-3-R-6H10H-
pyrimido[4rsquo5rsquo34]pyrazolo[51-c][124]triazine (12) N-(3-tert-butyl-48-dithioxopyrazolo[51-
c][124]triazin-7-yl)аmid metadithiophosphorous acid (9) (348 [M+]) was received from the
responding compounds (3)
The structures of the synthesized compounds are confirmed with spectral methods (IR H1-NMR-
mass spectra) and elemental analysis data
Compounds show weak antimicrobial activity
[1] Mironovich LM and Kostina MV Russian Journal of Organic Chemistry 2011 vol 47
12 P 1917
212
P101
HYBRID MATERIALS BASED ON COPPER AND PALLADIUM
COMPLEXES OF (110-PHENANTHROLYL)PHOSPHONATES FOR
CATALYSIS
AYu Mitrofanov1 AG Bessmertnykh-Lemeune
2 R Guilard
2 NS Goulioukina
1 IP
Beletskaya1
1 - AN Frumkin Institute of Physical Chemistry and Electrochemistry of RAS 31-4 Leninskiy p
Moscow 119071 Russia
2 - Institut de Chimie Moleculaire de Universite de Bourgogne (ICMUB) UMR CNRS 6302 9
avenue A Savary 21078 Dijon Cedex France
Considerable attention has been attached recently to the immobilization of transition metal
complexes onto solid supports to prepare advanced catalytic systems [1]
Using this approach it is
expected to increase catalyst stability and allow for catalyst recycling and product separation
Organophosphonates are of interest for this field due to their simple synthesis and high reactivity
towards various metal salts and alkoxides In fact different ligands can be easily decorated by the
phosphonate group for immobilization onto thermally and mechanically stable metal oxide
matrices Herein we describe the results of our studies on the functionalization of titania by
copper(I) and palladium(II) complexes with (110-phenanthrolyl)phosphonates (Pphen) recently
described by us (Figure)[2]
Figure Copper(I) and palladium(II) complexes with Pphen
The covalent grafting of the complexes was performed according to two routes The first one so-
called lsquolsquoone-potrsquorsquo synthesis involves a co-condensation step between a complex with an inorganic
precursor (titanium isopropoxide) according to the sol-gel technique In the second one so-called
lsquolsquopost-functionalizationrsquorsquo а chemical surface modification of a preformed mesoporous titanium(IV)
dioxide (SBET = 650 m2g) through chemical bonds between the hydroxyl groups covering the pore
surface and complexes is used The structural and textural properties of these hybrid materials will
be presented and explained based on a solution behavior of the studied complexes High catalytic
activity of newly synthesized hybrid materials in the palladium-free Sonogashira reaction the
copper-catalyzed boration of alkynes and Suzuki reaction are reported and examples of catalyst
recycling are given
Acknowledgements This work was carried out in the frame of French-Russian Laboratory
ldquoLAMREMrdquo of CNRS and RAS and supported by Russian Foundation for Basic Research (grant
12-03-93114)
[1] Suib S L New and Future Developments in Catalysis Elsevier Amsterdam 2013
[2] (a) Mitrofanov A Yu Bessmertnykh-Lemeune A Stern C Guilard R Gulyukina N S
Beletskaya I P Synthesis 2012 44 3805 (b) Mitrofanov A Yu Manowong M Rousselin
Y Brandes S Guilard R Bessmertnykh-Lemeune A Chen P Kadish K M
Goulioukina N Beletskaya I Eur J Inorg Chem 2014 DOI101002ejic201402161
213
P102
SYNTHESES STABILITIES AND REACTIVITIES OF
ALKYNYL(ARYL)IODONIUM SALTS
WJ Moran
University of Huddersfield Department of Chemistry Huddersfield UK
Iodonium salts are increasingly popular reagents in organic synthesis because of the range of useful
reactivities that they exhibit1 The most investigated iodonium salts are the diaryliodonium salts
which can in principal donate either of their aryl groups in reactions with nucleophiles (Scheme
1)2 In contrast alkynyl(aryl)- and alkenyl(aryl)iodonium salts only donate the alkyne or alkenyl
groups respectively This means that the aryl iodide group is essentially a spectator group in these
two types of iodonium salts However the effect of changing this spectator group on the reactivity
of these salts has not been studied3
Scheme 1 General reactivities of iodonium salts with nucleophiles highlighting the ldquospectatorrdquo role
of the aryl iodide in alkenyl- and alkynyl(aryl)iodonium salts
Our study on the preparation of a range of alkynyl(aryl)iodonium salts directly from terminal
alkynes and aryl iodides and the stabilities and reactivities of these salts will be discussed4
Surprisingly we found a marked increase in the stability and reactivity of iodonium salts derived
from 2-iodoanisole (Scheme 2) I will also present our results on generating alkynyl(aryl)iodonium
salts from alkynylsilanes and reacting them directly resulting in yield augmentations of up to 50
compared to the iodobenzene parent
Scheme 2 Direct syntheses of alkynyl(aryl)iodonium salts and the effect of the aryl iodide
substituents on stabilities and reaction yields 1 For reviews of iodonium salts in organic synthesis see a) M S Yusubov A V Maskaev V V
Zhdankin Arkivoc 2011 i 370 b) E A Merritt B Olofsson Angew Chem Int Ed 2009 48 9052 c)
T Okuyama Acc Chem Res 2002 35 12
2 M Fujita E Mishima T Okuyama J Phys Org Chem 2007 20 241
3 Selected examples of reactions with alkynyl(phenyl)iodonium salts a) B L Williamson P J Stang A
M Arif J Am Chem Soc 1993 115 2590 b) B L Williamson R R Tywinski P J Stang J Am
Chem Soc 1994 116 93 c) M Ochiai K Miyamoto T Suefuji S Sakamoto K Yamaguchi M
Shiro Angew Chem Int Ed 2003 42 2191 examples of reactions with alkenyl(phenyl)iodonium salts
d) M G Suero E D Bayle B S L Collins M J Gaunt J Am Chem Soc 2013 135 5332 e) T
Okuyama M Fujita Acc Chem Res 2005 38 679
4 D J Hamnett W J Moran manuscript submitted for publication
214
P103
MATHEMATICAL MODELING OF DYNAMICS OF PHOTOCHEMICAL
REACTIONS AT THE QUANTUM AND THE CLASSICAL DESCRIPTION
OF THE RADIATION FIELD
VA Morozov ND Chuvylkin EA Smolenskii
N D Zelinsky institute of organic chemistry Leninsky prospekt 47 119991 Moscow Russia
Are examples of differences between the results of using two methods of mathematical modeling of
dynamics of populations of the states of the molecule in photochemical reactions The first method
is based on the solutions of the Schrodinger equation for the probability amplitudes of the
population of states of the molecule and the radiation field is described by quantum theory When
using a three-level model of the molecule these solutions are obtained analytically The second
method is based on numerical solutions of the equations for the density matrix elements of the
molecule interacting with the classically described irradiation and phenomenological decay of
excited states of molecules The differences formalisms used methods and an underlying
conceptions of the physical sense of the light transformation by molecules in photochemical
reactions are discussed
215
P104
SYNTHESIS OF SPIROCYCLOPROPYL MALONYL PEROXIDE FROM
CYCLOPROPYL MALONIC ESTER
OM Mulina VA Vill AO Terentiev
ND Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences Laboratory for
Studies of Homolytic Reactions Moscow Russia
Cyclic diacyl peroxides were in use in oxidation reactions in the 1950-70s [1] At the present time
great attention is attracted to these compounds [2] An unique property of such spirocyclic
diacylperoxides as malonyl and phtaloyl ones is their capability to oxidate unsaturated compounds
without any catalysts alternatively to their linear analogues for example commercially available
benzoylperoxide and succinylperoxide and widespread peroxy cycles ozonides and tetraoxanes
Among malonyl peroxides a spirocyclopropyl malonyl peroxide is the activest and the most
frequently used oxidant It has the lowest molecular weight among familiar malonyl peroxides [2a]
and this fact makes the oxidation process more atom-efficient
The main procedure of synthesis of spirocyclopropyl malonyl peroxide 2 is the reaction of
spirocyclopropyl malonic acid with 90-98 hydrogen peroxide [3] or hygrogen peroxide and urea
hydrogen peroxide [2a] in the presence of methanesulfonic acid (Scheme 1)
In the present work we succeeded in synthesis of peroxide 2 in the reaction between
spirocyclopropyl malonic peroxide 1 which can be easily synthesised by alkylation of diethyl
malonic ester with 12-dichlorethane in high yields 85-88 and hygrogen peroxide and urea
hydrogen peroxide in the presence of methanesulfonic acid
This method makes the synthesis of spirocyclopropyl malonyl peroxide 2 dramatically easier
because it excludes come chemical and procedural steps
1 (a) W Adam J W Diehl J Chem Soc Chem Commun 1972 13 797-798 (b) C L Perrin
T Arrhenius J Am Chem Soc 1978 100 5249-5251
2 (a) J C Griffith K M Jones S Picon M J Rawling B M Kariuki M Campbell N C O
Tomkinson J Am Chem Soc 2010 132 14409-14411 (b) M Schwarz O Reiser Angew
Chem Int Ed 2011 50 10495-10497 (c) C Yuan A Axelrod M Varela L Danysh D
Siegel Tetrahedron Lett 2011 52 2540-2542
3 (a) W Adam R Rucktaumlschel J Am Chem Soc 1971 93 557-559 (b) M J Darmon G B
Schuster J Org Chem 1982 47 4658-4664
216
P105
HYPOTHETICAL REACTION MECHANISM OF H2-ASSISTED N-C6H14-
DENOX OVER AgAl2O3 CATALYSTS
AI Mytareva NA Sadokhina GN Baeva AYu Stakheev
ND Zelinsky Institute of Organic Chemistry Moscow Russia
Since Satokawa et al [1] discovered that the low temperature activity of AgAl2O3 in HC-SCR of
NOx can be boosted by addition of small amounts of H2 the nature of ldquohydrogen effectrdquo has been
studied intensely However the mechanism of H2-assisted HC-SCR of NOx is still debated and
several solutions have been proposed One of the possible pathways involves H2-promoted
formation of NO3oline surface species followed by their transformation to reactive NO2oline species which
further react with activated HCs In the present study in order to evaluate possible contribution of
this pathway into overall H2-assisted HC-SCR over AgAl2O3 we compared the rate of H2-assisted
C6H14 DeNOx in steady-state and the rate of NO3olinesurf reduction by C6H14 in the presence and the
absence of H2
It was repeatedly shown by FTIR and TPD that addition of H2 into reaction mixture results in the
intensive formation of NO3olinesurf located on Ag species and Al2O3 surface This process is very fast
and leads to the complete removal of NOx from the reaction mixture until saturation of the catalyst
surface is attained Surface reaction of NO3olinesurf species with the feed containing 1000 ppm C6H14
revealed their inertness with respect to HC reductant On the other hand surface reaction with NO or
H2 leads to NO3olinesurf rarr NO2olinesurf transformation as evidenced by intensive NO2 evolution and in situ
XPS data It should be noted that NO was found to be more effective in NO3olinesurf rarr NO2olinesurf
transformation as compared to H2 particularly at the reaction temperature below ~ 180degC
Transformation of NO3olinesurf into NO2olinesurf greatly enhances reactivity of surface N-containing
species and NO2olinesurf species are rapidly reduced into N2 in the course of the surface reaction with
300 ppm C6H14 + 1000 ppm H2 It was found that the rate of NO3olinesurf reduction by hydrocarbons in
the presence of H2 is identical to the rate of H2-HC-SCR of NOx in steady state This observation
suggests significant contribution of NO3olinesurf reduction in the rate of the overall HC-SCR mechanism
at 150-300 degC These results appear to be in a good agreement with the literature data on the
transient measurements of H2-assisted DeNOx over AgAl2O3 [2-3]
References
[1] S Satokawa Chem Lett 2000 29 294
[2] JP Breen R Burch and CJ Hill Catal Today 2009 145 34
[3] S Chansai R Burch Ch Hardacre J Breen and FJ Meunier J Catal 2010 276 49
217
P106
DEPENDENCE OF THE SPECIFIC ACTIVITY ON THE PLATINUM
PARTICLE SIZE IN THE DEEP OXIDATION OF C1 - C6 NORMAL
ALKANES
AM Batkin1 AYu Stakheev
1 IE Beck
2 NS Teleguina
1 GO Bragina
1 VI Zaikovsky
2 YuV
Larichev2 VI Bukhtiyarov
2
1 - ND Zelinsky Institute of Organic Chemistry Moscow Russia
2 - Boreskov Institute of Catalysis SB RAS Novosibirsk Russia
The deep oxidation of volatile organic compounds (VOCs) over supported catalysts based on noble
metals (Pt Pd) is among the main exhaust gas aftertreatment technology for mobile machinery and
stationary applications One of the most important factors influencing the efficiency of noble metal
catalyst is the size of metal particles High Pt dispersion improves utilization of noble metal since
increases the fraction of atoms accessible for a reaction On the other hand very small metal
particles may be ineffective in the reactions requiring multi-atomic surface active sites (structure-
sensitive reactions) The influence of the metal particle size on the total and specific catalytic
activity (SCA or atomic activity) in deep oxidation was extensively studied A comparison between
experimental data obtained by independent authors allowed us to suppose that the structural
sensitivity of deep oxidation and the size effect of the platinum particles on the specific catalytic
activity can also be dependent on the structure (first of all on the size) of the hydrocarbon
molecule
In this study we compared the effect of Pt particle size on the activity in catalytic combustion of
normal alkanes with different hydrocarbon chain length (C1 ndash C6) over a series of 08 PtAl2O3
with different average Pt particle sizes ranging from 1 to 12 nm
It was established that the range in which specific catalytic activity changes depends substantially
on the carbon chain length of the n-alkane In the oxidation of CH4 or С2H6 atomic activity
increases approximately 2ndash 3 times as the Pt particle size changes from 1 to 11 nm In propane
oxidation SCA increases approximately by a factor of 5ndash6 whereas in the oxidation of n-C4H10 and
n-C6H14 the specific activity increases 20 and 25 times respectively Thus the structural sensitivity
of the deep oxidation of n-alkanes increases with an increase in the size of the hydrocarbon
molecule being oxidized
It was found that the catalysts with the maximum degree of dispersion of platinum (dPt = 1ndash2 nm)
exhibit the highest total activity in the oxidation of small molecules The catalysts consisting of
larger Pt particles (3ndash6 nm) are most active in the oxidation of longer n-butane and n-hexane
molecules whereas the activity of the finer catalysts is substantially lower
Acknowledgement Financial support by RFBR grant 12-03-01104-a is gratefully acknowledged
218
P107
COMPOSITE CATALYSTS [Fe-BETA + REDOX] FOR COMBINING
CATALYTIC PROCESSES 1) NH3-SCR AND NH3-SLIP REMOVAL
2) NO TO NO2 OXIDATION AND FAST SCR
AI Mytareva1 GN Baeva
1 DA Bokarev
1 AYu Stakheev
1 P Selvam
2
1 - ND Zelinsky Institute of Organic Chemistry Moscow Russia
2 - Indian Institute of Technology-Madras National Centre for Catalysis Research and Department
of Chemistry Chennai India
Combining several catalytic processes over single catalyst is the general trend in modern
heterogeneous catalysis We explored this approach to develop catalytic systems for environmental
protection ndash selective catalytic reduction of NOx by ammonia (NH3-SCR) NH3-SCR is of
theoretical and practical interest for abatement NOx emission from automotive (diesel engines) and
stationary (power plants) sources Recently NH3-SCR can be achieved by using catalytic systems
based on Fe-Beta or Cu-Beta However these catalysts have two main drawbacks 1) insufficient
NOx conversion at ldquocold-startrdquo condition (150-250ordmC) and 2) NH3-slip problem due to incomplete
conversion or exhaust temperature upswings We attempted to solve these problems by using
composite catalysts [Fe-Beta + RedOx] comprising NH3-SCR and RedOx functions
1 Combining NH3-SCR and NH3-slip removal
According to our recent results Fe(Mn)MCM-48 can be used as RedOx components due to high
activity in NH3 oxidation process Therefore composite catalyst was prepared by mechanical mixing
of Fe-Beta and Fe(Mn)MCM-48 components
It was shown that mechanical mixing of Fe-Beta with Fe(Mn)MCM-48 allowed us to combine
favorable NH3-SCR performance of Fe-Beta (1) and activity of Fe(Mn)MCM-48 in NH3
oxidation (2) in one catalytic brick
2 NO + 2 NH3 + frac12 O2 rarr 3 H2O + 2 N2 ndash over Fe-Beta (1)
4 NH3 + 3 O2 rarr 2 N2 + 6 H2O ndash over Fe(Mn)MCM-4 (2)
Varying the ratio of the components optimum SCR and NH3-slip removal performance of
composite catalyst can be achieved Moreover [Fe-Beta + Fe(Mn)MCM-48] demonstrates low N2O
emission
2 Combining NO oxidation and NH3-SCR
CeO2-ZrO2 demonstrates high activity in NO oxidation to NO2 Furthermore it was found that the
activity can be further boosted viz modification by manganese In this study MnCeO2-ZrO2 was
mixed with Fe-Beta for enhancing low-temperature NH3-SCR activity of zeolite component
It was found that mixing of zeolite and RedOx component leads to a significant increase in NOx
conversion at 150-250ordmC This synergistic effect can be attributed to combination of two processes
NO oxidation over MnCeO2-ZrO2 (3) followed by the Fast SCR (4) on Fe-Beta
2 NO + O2 rarr 2 NO2 ndash over MnCeO2-ZrO2 (3)
NO + NO2 + 2 NH3 rarr 3 H2O + 2 N2 ndash over Fe-Beta (4)
Acknowledgments
This work was supported by the Russian Foundation for Basic Research (Grant 13-03-
92711IND_a) and Department of Science and Technology New Delhi (Grant INTRUSRFBRP-
152)
A Mytareva is grateful to Haldor Topsoslashe AS for financial support in the framework of PhD
student support programme
219
P108
NON CATALYTIC EFFICIENT APPROACH TO SUBSTITUTED 2349-
TETRAHYDRO-1H-XANTHEN-1-ONES - A GROUP OF ORALLY ACTIVE
NEUROPEPTIDE Y Y5 RECEPTOR ANTAGONISTS FROM
SALICYLALDEHYDES AND DIMEDONE
RF Nasybullin OO Sokolova MN Elinson
ND Zelinsky Institute of Organic Chemistry Moscow Russia
Functionally substituted tetrahydro-1H-xanthen-1-ones have received considerable attention in the
field of medicinal chemistry due to their useful biological properties and applications [1] Recently
it has been found that tetrahydro-1H-xanthen-1-ones are orally active and selective Y5 antagonists
[2] Known methods for the synthesis of tetrahydro-1H-xanthen-1-ones have its merits and suffer
from disadvantages such as long reaction times moderate yields or complicated work-up
procedures Thus the development of an efficient and facile method for the synthesis of tetrahydro-
1H-xanthen-1-ones is in high demand
In the present study we report our results on thermally induced non catalytic transformation of
salicylaldehydes and dimedone into substituted tetrahydro-1H-xanthen-1-ones (Scheme 1) The
reaction is performed in ethanol under 3 min reflux Corresponding 9-(2-hydroxy-44-dimethyl-6-
oxo-1-cyclohexen-1-yl)-33-dimethyl-2349-tetrahydro-1H-xanthen-1-ones were formed in
excellent 85-95 yields
Scheme 1
In conclusion simple non catalytic system can produce under neutral conditions a very fast
(3 min) and selective transformation of salicylaldehydes and dimedone into tetrahydro-1H-xanthen-
1-ones ndashndash the orally active and selective Y5 antagonists and the promising heterocyclic compounds
for different biomedical applications The procedure utilizes simple equipment it is easily carried
out and is valuable from the viewpoint of environmentally benign diversity-oriented large-scale
processes
Acknowledgements
The authors gratefully acknowledge the financial support of the Russian Foundation for Basic
Research (Project No 14-03-31918)
References
1 H KWang S L Morris-Natschke K H Lee Med Res Rev 1997 17 367
2 S Mashiko A Ishihara H Iwaasa H Sano Z Oda J Ito M Yumoto M Okawa J Suzuki T
Fukuroda M Jitsuoka N R Morin D J MacNeil L H T Van der Ploeg M Ihara T
Fukami A Kanatani Endocrinology 2003 144 1793
220
P109
SOLUBILITY AND STRUCTURE OF CHITOSAN IN AQUEOUS MEDIA OF
VARIOUS ACIDITY MOLECULAR DYNAMIC STUDY
VS Naumov SK Ignatov AG Razuvaev AE Mochalova IA Glazova LA Smirnova
NI Lobachevsky State University of Nizhny Novgorod Russia
Polyaminoglucanes particularly chitosan (poly-14-(N-acetyl)-β-D-2-glucopyranoseamine) are
considered today as promising means for encapsulating the protein-contaning drugs ensuring their
transport inside an organism This task is however complicated by the lack of information about
the structure of the chitosan complexes in aqueous solutions their thermodynamic properties and
kinetics of complexation In particular the structure of chitosan chains in the aqueous solution
based on the data of electron microscopy was a subject of discussion [1] Data on the complexation
constants with various protein agents are virtually absent and the details of dissolution kinetics are
mostly studied on the basis of formal kinetic approach or without adrressing to the protonation
effects [23] In the present study we use the molecular dynamics (MD) simulations in order to
elucidate the details of nanocrystalline chitosan dissolution the influence of amino group
protonation and kinetics of its dissolution at various acidity of aqueous media The model system
was a chitosan nanocrystal surrounded by the water molecules (SPC water model) and counterions
(Cl-) compensating the protonated amino group charges The simulation box size was 124 x 117 x
208 nm (~302000 atoms in total ~100000 water molecules) The nanocrystal was consisted of 8
chains of 20 monomeric units (32 kDa per chain) The initial crystal structure was constructed on
the basis of XRD data [4] Some of amino groups were protonated in the crystal with the
protonation degree (PD) corresponded to the pH values from 53 to ~72 Calculations were
performed with GROMACS 461 using the force field GROMOS 53A6Carbo [5] specially
improved for better polyaminoglycane unit description Force field modification was perfromed on
the basis of quantum chemical calculations (HFSTO-3GB3PW916-31++G(dp)) Simulation
period was up to 10 ns with integration step of 1 fs in the NVT-ensemble at 300K controlled by the
Berendsen thermostat It was found that at the beginning of dissolution process the nanocrystal
undergoes the remarkable twist-like deformation resulting to the compact bunches of chitosan
chains Then at PDgt03 the bunches undergo slow dissociation which rate is determined by the
quantity of protonated amino groups The time-dependency of dissolution degree (measured as an
average distance between chains) is almost linear during 10 ns of simulations The dissolution rate
estimated as the time derivative of average distance between chains is also linearly dependent on
PD with threshold of dissolution about PD=03 (pH~68) which agrees well with available
experimental data The final structures of chitosan after 10 ns of dissolution in aqeous media of
various acidity are shown in Figure
[1] Pedroni VI Schulz PC Gschaider ME Andreucetti N Colloid Polym Sci 2003 282 100
[2] Franca EF Lins RD Freitas LCG Straatsma TP J Chem Theory Comput 2008 4 2141
[3] Franca EF Freitas LCG Lins RD Biopolymers 2011 95 448
[4] Yui T Imada K Okuyama KObata YSuzuki KOgawa K Macromolecules 1994 27 7601
[5] Hansen HS Huumlnenberger PH J Comput Chem 2011 32 998
This work was supported by the RFBR (Project No 14-03-00585 14-03-31981)
221
P110
THE STEAM OSMOTIC ENGINE WITH THE INCREASED EFF TO 50
PA Nazarov
Russian Chemical Technology University named after DI MendeleevChair of Processes and
devices of chemical technology positionMoscowRussia
The evolution of heat osmotic engine [2] on the prototype[1] is to increase the temperature
(T1=380С) of the left part of the circuit(fig1) the engine in changing the phase state of the water
from liquid to gas but also adding a second stage of desalination by electrodialysis
Due to the process steam or osmosis process of rapid diffusion of water vapor molecules through
the membrane into the liquid solution inside the reactor 3(fig1) osmosis increases the specific
power of the engine(Wkgengine) as well as its efficiency
Steam osmotic engine[2] repeats energy cycle thermal power plant but through a process of
steam osmosis and because of the lack of vapor condensation (in the cooler) its efficiency is much
higher
Ideal efficiency manual 2-nd Carnots theorem is(fig1)
EFF= [(T1ndashT2)T1]х100 = [(380Сndash20С)380С]х100=[(653ndash293)653]х100=55 (1)
Given the mechanical losses in the pump Pump1 2 formula for calculating the efficiency takes the
form
EFF мах =(NndashWpumps)∆Q= [(T1ndashT2)T1]ndashWpumps= [(P1osmosisndashP2reverse osmosis)P1osmosis]ndashWpumps (2)
Where N [W] - output power of osmotic (hydraulic) flow ∆Pturbines=2241at ΔQ [W] - The amount
of heat in heat generators 12 to keep the system in a given thermal regime (the left side of the
technological scheme T1=380C=653k right side T2=20C=293k) Wpumps [W] - power pumps12
Steady state operation of the scheme of steam osmotic engine T1=379-380C T2=20-40C
fig1
References
1 Patent of USA 4193267 on 18031980 Metod and apparatus for generating power utilizing
pressure-retarted osmosis Inventor Sydney Loeb the Bulletin 1877989 15021978
2 The application for the patent of the Russian Federation 2014108948 from 11032014
laquoMethod of reception of mechanical energy and the steam osmotic engine for its realisationraquo the
applicant and the legal owner Nazarov P A
222
P111
THE UNSATURATED CARBON-CARBON BOND HYDROGENATION IN
PRESENCE OF NANOPARTICLES OF THE Fe-Ni GROUP
DN Nebykov VM Mokhov YuV Popov
Volgograd State Technical University Chemical Technology Faculty Volgograd Russia
The hydrogenation of unsaturated substances and arenes is a widely used industrial process but it
proceeds in harsh conditions or requires using of expensive catalysts We discovered some methods
giving an ability to carry out the reduction of different substituted alkenes and arenes without using
of high temperatures and pressures or expensive materials by means of using ferrous cobalt or
nickel nanoparticles as catalysts
The advantage of methods is in combination of metal nanoparticles synthesis and organic substance
hydrogenation The nano-catalyst is formed from inexpensive metal salts by their reduction with
complex borohydrides or alumohydrides or by hydrazine hydrate in solutions in some cases
proceeds in situ hydrogenation of unsaturated bonds
The essential interest deserves a method of liquid phase alkenes hydrogenation with gaseous
hydrogen at atmospheric pressure which is a widely used and inexpensive industrial reagent Using
of simply obtained from accessible and inexpensive substances metal nanoparticles is able to
decrease the cost and energy losses comparing to traditional hydrogenation methods
The investigations showed an ability of the carbon-carbon unsaturated bond hydrogenation at very
smooth conditions - atmospheric pressure and near room temperatures Also was found that change
of hydrogenating agent catalyst and its preparing conditions makes possible to direct the process
selectivity and also to reduce some functional groups As starting materials for hydrogenation were
used different derivatives of norbornene styrene linear and cyclic alkenes heterocyclic
compounds
References
1 Colloid and nanodimensional catalysts in organic synthesis I Investigation of hydrogenation
selectivity of unsaturated compounds with hydrazine hydrate and aluminum hydride Popov
YuV Mokhov VM Nebykov DN Russian Journal of General Chemistry - 2014 - Vol 84
No 3 - C 444-448
2 Colloid and nanodimensional catalysts in organic synthesis II The hydrogenation of alkenes
with hydrogen at atmospheric pressure Popov YuV Mokhov VM Nebykov DN Russian
Journal of General Chemistry - 2014 - Vol 84 No 4 - C 622-628
3 Hydrogenation of unsaturated carboxylic acids Mohov VN Popov YV Nebykov DN
Izvestiya VolGTU Series ldquoChemsitry and technology of organoelemnt monomers and polymeric
materialsrdquo Iss 12 MezhvussbnauchstVolGTU ndash Volgograd 2014 N7 (134) ndash C 60-63
223
P112
SYNTHESIS AND INVESTIGATION OF FUNGICIDAL ACTIVITY OF 6-
BROMO-4-HYDROXY-2-PHENILINDOLE
OD Neverova MD Dutov SA Shevelev GV Bastrakova OV Serushkina KE Aisina SV
Popkov
N D Zelinsky institute of organic chemistry Leninsky prospekt 47 119991 Moscow Russia
Recently we showed high fungicidal activity of the 2-aryl-4-hydroxy-6-nitroindoles [1] The
presence of the nitro group in these compounds of course reduces their value as fungicides as in
the case of use as agricultural agents and in the case of drugs Therefore it is very important task to
replace the nitro group to an appropriate electronegative substituent as which by analogy with
Arbidol we have chosen a bromine atom Synthesis of the title compound (1) was carried out as
follows
It is shown that 6-bromo-4-hydroxy-2-phenylindole outperforms standard triadimefon by
fungitoxicity with respect to all the examined fitopatagence not inferior nitro analog
Compound Mycelium growth inhibition (С = 30 μg mL-1
)
Vi Rs Fo Fm Bs Ss
100 92 88 100 95 100
89 100 88 100 100 100
Triadimefon 42 66 60 79 71 47
The authors thank the Russian Foundation for Basic Research (Grant No 13-03-01276) for financial
support
[1] G V Kokurkina M D Dutov S A Shevelev S V Popkov A V Zakharov and V V
Poroikov European Journal of Medicinal Chemistry 2011 46 4374-4382
224
P113
THEORETICAL STUDY OF MULTISTEP MECHANISM OF THERMAL
FRAGMENTATION OF O-NITRO TOLUENE
EV Nikolaeva AG Shamov GM Khrapkovskii
Kazan National Research Technological University Catalisis Department Kazan Russia
A mechanism which is believed to be involved in thermodistruction of o-nitrotoluene (I) and other
nitroarenes bearing hydrogen-containing substituent in ortho-position to nitro group includes the
formation of its aci-form at the first step At the same time significant differences in activation
enthalpies ( H = Ea ndash RT) of thermodistruction of compound I were observed by different authors
Thus in the temperature interval 300-350оС H equals 1728 kJmol[4] 350-420
оС H =
2016 3 kJmol 797-907оС H = 2062 kJmol Results of theoretical investigation of the
thermodistruction mechanism of compound I can be presented as the following scheme
The data on relative enthalpies of formation of transition states of reactions ( Hf enthalpy of
formation of o-nitrotoluene was selected as zero) for this scheme provided in the literature suggest
that it should terminate at the limiting step of hydrogen atom transfer between two oxygens in the
group =N(O)OH (process III VI) Possibility of further reactions remained unclear The
investigation of the specified sequence of transformation of o-nitrotoluene by B3LYP6-
31+G(2dfp) demonstrated that this scheme can be realized if isomerization III IV proceeds as a
rotation of =N(O)OH around С=N bond For this process Hf equals 188 kJmol The limiting
steps are elimination of water (V VII) or hydroxyl radical (V VI) from 21-benzisoxazol-
2(3H)-ole (V) with barriers being equal 1930 and 2049 kJmol respectively That is at lower
temperatures a more probable would be the realization of the process V VII since for it Hf
correlates well with experimental estimation of 2016 3 kJmol At higher temperatures there is an
opportunity for elimination of OH from compound V (V VI) since for it Hf correlates well
with experimental estimation of 2062 kJmol In favor of this conclusion is the systematic character
of deviations (1-9 kJmol decrease) of calculated values of activation enthalpies of primary act and
specified steps from experimental data
1 VG Matveev VV Dubihin GM Nazin Izv Acd Nauk USSR Ser chem 2 474-476 (1978)
2 GMKhrapkovskii AGShamov EVNikolaeva DVChachkov RussChemRev 78 10 903-943
(2009)
3 Y Y Maksimov Zh Phys Chem XLIII 3 725-729 (1969)
4 TB Brill KJ James Chem Rev 93 2667-2692 (1993)
5 W Tsang D Robaugh WG Mallard J Phys Chem 90 5968-5973 (1986)
6 YV Ilrsquoichev J Wirz J Phys Chem A 104 7856-7870 (2000)
7 SC Chen SC Xu E Duau MC Lin J Chem Phys A 110 10130-10134 (2006)
8 G Fayet L Joubert P Rotureau C Adamo J Phys Chem A 113 13621-13627 (2009)
9 EV Nikolaeva DV Chachkov AG Shamov GM Khrapkovskii Vestnik NovGU 2 73 76-82 (2013)
225
P114
OPTICAL ACTIVE BIS-IMINE RHODIUM(I) COMPLEXES IN TRANSFER
HYDROGENATION OF PROCHIRAL C=O BONDS
LO Nindakova AV Khatashkeev NM Badyrova IA Ushakov EKh Sadykov
Irkutsk State Technical University Physical-technical Institute Irkutsk Russia
Rhodium (1+) complexes with bis-aldimine ligands on the basis of (RR)-12-cyclohexanediamine
(1) were tested in the asymmetric transfer hydrogenation of ketones and ketoacids with
isopropanol as hydrogen source under basic conditions The catalystsubstrate ratio was 1170-340
Ligands (1а-1с) were synthesized by the condensation reaction of diamine 1 with aldehides 2-
pyridinecarbaldehyde 2-quinolinecarbaldehyde and 2-thiophene-carbaldehyde following the
scheme
Rrsquo- =
Rhodium complexes were used as catalysts for this reaction it was confirmed by 1Н and
13С HMR
that this complexes were formed in situ from the reaction of [Rh(15-COD)Cl]2 and ligands 1a-1с
TOF and TON values are higher for ligands that synthesize from 2-pyridinecarbaldehyde (250 h-1
340) and from 2-quinolinecarbaldehyde (109 h-1
170) the lowest values were obtained for bis-
aldimine based on 2-thiophene-carbaldehyde (16 h-1
43) The excess formation of R-(+)-
enantiomer of 1-phenylethanol and R-(-)-methyl mandelate is observed for all Rhodium complexes
But the all used catalytic systems are slightly enantioselective (prior to 20 of ee) similar result
was obtained using Ir - and Ru -bis(oxazoline) catalytic system [1]
[1] Goumlmez M Jansat S Muller G Bonnet M C Breuzard J AJ Lemaire M J Organomet
Chem 2002 659 186-195
226
P115
STRUCTURAL ANALYSIS OF IODINE ADDUCTS WITH
HETEROAROMATIC N-OXIDES
VV Romanov1 YP Nizhnik
1 AV Ryzhakov
2 LL Rodina
3
1 - Petrozavodsk State University Petrozavodsk Russia
2 - Karelian Research Center RAS Petrozavodsk Russia
3 - St Petersburg State University St Petersburg Russia
Heteroaromatic N-oxides contain two potential donor centers capable to interact with Lewis acids
such as halogen bond donors -system of the aromatic rings and the oxygen atom of N-oxide
group According to the HSAB principle the iodine as a soft Lewis acid might interact on both
donor centers however the literature and our IR-spectroscopy data unambiguously indicate the
oxygen atom as a donor center
Yet a half-century ago T Kubota [1] questioned the exact geometry of iodine adducts of N-oxides
due to potentially different hybridization types of oxygen atom Actually owing to an ambivalent
character of the group NndashO in the heteroaromatic N-oxides the oxygen atomrsquos hybridization might
be characterized by the two extreme cases ndash sp3 or sp
2
Single X-ray data obtained by us for the adducts of iodine with pyridine 4-methylpyridine and 4-
chloroquinoline N-oxides have clearly demonstrated the sp3-character of the oxygen atom in the
complexes and the absence of any -interaction In the both cases for pyridine N-oxides the
structure of the adducts includes infinite quasi one dimensional chains of alternating D and A
moieties ( IndashI O IndashI O ) In the case of the adduct of 4-chloroquinoline N-oxide with iodine
(see the picture) the individual adduct molecule may be distinguished within the crystal lattice To
estimate the possibility of existing different conformations of the adduct (sp3 or sp
2) on the base of
its crystal structure the energy profile of the structure was calculated in Hyperchem program as the
dependence of the potential energy on the dihedral angle (IndashIndashOndashN) ndash (quinoline ring)
Two distinct barriers have been observed at 0o
( E = 357 Kcalmol corresponds to the structure
where iodine is in a close proximity to H8) and 180o ( E = 37 Kcalmol iodine is in a close
proximity to H2) The real X-ray structure (dihedral angle 117 o
( E = 025 Kcalmol) is similar to
the calculated conformer (dihedral angle 131 o
( E = 0 Kcalmol)) Obtained data indicate that
potential ldquosp2-stereoisomersrdquo are not favorable energetically due to probably the sterical factors and
should not be observed at least in the case of ldquostrongrdquo adducts with bulky Lewis acids
[1] T Kubota J Amer Chem Soc 1965 87(3) P458-468
227
P116
COPPER CATALYZED CYCLOPROPYL-ALLYLIC RING-OPENING
TRANSFORMATIONS OF GEM-CHLOROFLUORO- AND GEM-
BROMOFLUOROCYCLOPROPANES PREPARATION OF 2-
FLUOROALLYL HALIDES
MA Novikov NV Volchkov MB Lipkind OM Nefedov
N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russian
Federation
Cyclopropyl-allylic ring-opening transformation of gem-chlorofluoro- and gem-bromofluoro-
cyclopropanes widely available by carbene cyclopropanation of corresponding alkenes is an
attractive tool for preparation of 2-fluoroallylic compounds that are known to possess a wide range
of biological activities
Ability of copper(I) compounds to catalyze cyclopropyl-allylic isomerization of gem-chlorofluoro-
and gem-bromofluorocyclopropanes was found and an effective route to 2-fluoroallyllic chlorides
and bromides was developed
R 2
R 1 R 3
R 4
F X
R 1
R 2
R 3
R 4
C F X
R 2
R 1
F
X
R 3 R 4
X = C l B r
R 1 -R 4 = H C H 3 -(C H 2 )n - (n = 2 -4 ) P h -C H = C H 2 c -C 3H 5 C l
C u X M eC N
o r
(N H C )C u X d io x an e
8 0 -1 0 0 degC
Thus from alkyl- aryl chloro substituted gem-chlorofluoro- and gem-bromofluorocyclopropanes
their bicyclic and spiro-substituted derivatives in presence of CuX or (NHC)CuX (NHC mdash N-
heterocyclic carbene) in MeCN or 14-dioxane at elevated temperatures corresponding 2-
fluoroallyllic chlorides and bromides could be prepared In the case of vinyl substituted gem-
chlorofluorocyclopropane 5-chloro-2-fluoropenta-13-diene forms as a major product Isomerization
of gem-chlorofluoro-11rsquo-bi(cyclopropane) proceeds via successive opening of both cycles leading
to 6-chloro-2-fluorohexa-13-diene as an only product
References
1) N V Volchkov M A Novikov M B Lipkind and O M Nefedov Mendeleev Commun
2013 23 19ndash21
2) M A Novikov N V Volchkov M B Lipkind and O M Nefedov Russ Chem Bull 2013
62 71ndash82
228
P117
DESIGN SYNTHESIS AND BIOLOGICAL EVALUATION OF P-
GLYCOPROTEIN INHIBITORS FOR MODULATION AND PREVENTION
OF MULTIDRUG RESISTANCE
M Sagnou1 X Alexiou
1 ES Kolotova
2 AA Shtil
2 AA Zeifman
3 IJ Titov
3 OV Stroganov
3
VV Stroylov3 IV Svitanko
3 FN Novikov
3 GG Chilov
3
1 - Demokritos National Research Center Greece
2 - Russian Scientific Oncology Center RAS
3 - N D Zelinsky institute of organic chemistry Russia
Multidrug resistance (MDR) mediated by P-glycoprotein (one of ATP-binding cassette (ABC)
transporters) through efflux of antineoplastic agents from cancer cells is a major obstacle to
successful cancer chemotherapy The inhibition of P-glycoprotein (P-gp) is thus a logical approach
to circumvent MDR There has been intensive research effort to design and develop novel inhibitors
for the P-gp and other ABC transporters to achieve this goal Complex in silico P-gp inhibition
model was developed in the present study using the pharmacophore ensemblesupport vector
machine scheme (to take into account the promiscuous nature of P-gp) molecular docking and
molecular dynamics approach (to predict ligand binding pose in huge P-gp hydrophobic cavity) and
free energy perturbation methods (FEP to accurate estimation of ligand-binding affinities) Two
series of novel P-gp inhibitors (based on curcumine scaffold) was designed synthesized and
evaluated in doxorubicin accumulation and cytotoxicity tests on chronic myeloid leukemia cell line
К562Dox with MDR phenotype
During the first round of optimization we discovered novel P-gp inhibitors that bind to the active
site of the enzyme and have activity comparable to clinical P-gp blocker verapamil We showed that
that hydrogen bonds with residues T837 and Q737 and hydrophobic and stacking interactions with
residues P770 Y307 and P994 play significant role in ligand binding We demonstrated that for
correct predictions of relative binding energy by FEP it is necessary to carry out an explicit account
of the solvent since the bridging water molecules significantly contribute to the energy of
formation of the protein-ligand complex
In the second round of optimization we discovered P-gp inhibitors that were to verapamil and
comparable with P-gp inhibitors in clinical trials We demonstrated that these compounds do not
exhibit the toxicity at concentrations up to 50 uM and have more than 100-fold lower IC50 in
doxorubicin cytotoxicity tests on К562Dox with MDR phenotype
229
P118
SELECTIVE HYDROGENATION OF UNSATURATED ALDEHYDES ON
THE COMPOSITE Pt-BASED NANOCATALYSTS A QUANTUM
CHEMICAL STUDY
AI Okhapkin1 OB Gadzhiev
1 AE Masunov
2 S Kunz
3 M Baumlumer
3 SK Ignatov
1
1 - NI Lobachevsky State University of Nizhny Novgorod Chemistry Department Nizhny
Novgorod Russia
2 - University of Central Florida Chemistry Department Orlando USA
3 - University of Bremen Institute for Applied and Physical Chemistry (IAPC) Bremen Germany
Selective hydrogenation of unsaturated aldehydes to alcohols is a key process in fabrication of
fragrance components for the modern cosmetology and perfume industry Since the selective oxo-
group hydrogenation is thermodynamically unfavorable due to the presence of the C=C bond the
industrial process is indirect complicated and expensive Recently a novel type of catalyst was
proposed that shows enhanced selectivity towards unsaturated alcohols It is using metal-oxide
supported Pt-nanoparticles with chemically modified surface In a present work the elementary
steps of such a catalytic reaction ie propenal and croton aldehyde hydrogenation were studied
within the cluster models of Pt surface using the DFT quantum chemical calculations (BLYP and
PBE density functionals in conjunction with the CRENBS or LANL2DZ pseudopotentials for Pt
atoms and 6-31G(dp) basis set for the remaining atoms) The clusters Pt8 Pt13 and Pt25 consisting
of two layers of Pt atoms were used as models for the Pt nanoparticle surface The diameter of the
Pt25 cluster is about 12 Aring which is close to the size estimated for the experimentally studied Pt
nanoparticles (18plusmn3Aring) [1] The different spin states of the clusters were considered (spin
multiplicity up to 11) The adsorption of reagents (H2 and aldehydes) and the organic ligands
working as orienting agents ensuring the reaction selectivity (BuSH Bu = n-C4H9) were studied as
initial steps of the catalytic process The various kinds of adsorption were studied (1) physical
adsorption of H2 on different sites of Ptn clusters (2) dissociative chemisorption of H2 resulting in
the Pt-adsorbed H atoms (3) chemisorption of ligands forming the Ptn-SBu structures and the
neighboring ndashSBuH adsorbed pairs (4) aldehyde adsorption on the neat Pt surface and the surface
partially occupied by the H atoms and the ndashSBu and ndashSBuH groups For all these pre-reaction
surface complexes the molecular structures adsorption energies and vibrational frequencies were
studied It was found that the ground state of the Pt25 clusters is the quintet one with the typical
spread of energies in lower spin states (M=135 and 7) of about 3 kcal mol-1
The H2 physical
adsorption energy is about 06-18 kcal mol-1
depending on the adsorption site The dissociative
adsorption energy of H2 was estimated to be 5-9 kcal mol-1
which is in reasonable agreement with
experimental values (~16 kcal mol-1
)[2] At the same time the ndashSBu group formation energy was
estimated as 30-56 kcal mol-1
depending on the adsorption site Their estimated surface coverage of
about 49 monolayer is in reasonable agreement with the experimentally observed dependence of
hydrogenation kinetics on the surface coverage [1] The kinetic barriers of the surface migration of
adsorbed H atoms and various hydrogenation pathways are discussed on the basis of the different
theoretical estimates
1 L Altmann S Kunz M Baumlumer J Phys Chem C 2014 118 8925-8932
2 PR Norton JA Davies TE Jackman Surf Sci 1982 121 103-110
The work was partially supported by the Russian Foundation for Basic research (project No 14-03-
00585) OBG and AIO are thankful to DAAD for the travel grants support
230
P119
NMR DIFFERENTIATION OF CHIRAL ALCOHOLS AND AMINES USING
SELENIUM-BASED CHIRAL PROBES
NV Orlov VP Ananikov
Zelinsky Institute of Organic Chemistry RAS Russia Moscow Leninsky pr 47 119991
Modern NMR spectroscopy is a powerful tool for structure elucidation of complex organic
molecules including natural products1 An important issue in this field is analysis of complex
mixtures of chiral compounds and determination of enantiomeric composition of each individual
molecule Utilization of chiral auxiliary reagents allows to efficiently differentiate enantiomers in
NMR spectra2 Besides continuous progress in development of chiral auxiliaries and derivatization
protocols made it possible to obtain diastereomers suitable for NMR analysis within minutes
directly in NMR tube excluding isolation and purification steps3 Nevertheless analysis of mixtures
of several chiral compounds is still a complicated task4
Recently we have developed simple synthetic routes to several selenium-based chiral probes which
readily react with chiral alcohols and amines directly in an NMR tube (Scheme 1 left) followed by
determination of their enantiomeric composition using 77
Se NMR spectroscopy5 In this case only
signals of selenium-containing diastereomers formed are observed in the spectra thus simplifying
assignment procedure
Scheme 1 DCC-promoted in tube derivatization of chiral alcohols and amines with chiral probes
R-ArSePA (left) and examples of spectral data - structure relationship using R-(4-
chlorophenylselanyl) propionic acid (right)
Now we have revealed that the diastereomers formed can be efficiently differentiated in 77
Se NMR
spectra depending on the nature of substituents at stereogenic center of analyzed chiral aclohols and
amines (Scheme 1 right) This observation gives possibility to perform preliminary structure
elucidation in several minutes and to analyse complex mixtures using a single 1D NMR experiment
Scope and limitations of this approach to various chiral alcohols and amines will be presented in the
poster
Acknowledgments This work was supported by RFBR (project No 12-03-01094)
1 Breton R C Reynolds WF Nat Prod Rep 2013 30 501
2 Wenzel T J Top Curr Chem 2013 341 1
Chem Rev 2012 112 4603
4 Novoa-Carballal R Fernandez-Megia E Jimenez C Riguera R Nat Prod Rep 2011 28
78
5 Orlov N V Ananikov V P Chem Commun 2010 46 3212
231
P120
NEW LIFE FOR OLD REACTION SYNTHESIS OF THIAZOLIDINES VIA
REGIOSELECTIVE ADDITION OF UNSYMMETRIC THIOUREAS TO
MALEIC ACID DERIVATIVES
AS Pankova MA Kuznetsov
Saint Petersburg State University Insitute of Chemistry Saint Petersburg Russia
Thiazolidine derivatives and in particular thiazolidinylacetic acids are highly valuable scaffolds for
medicinal and bioorganic chemistry as can be exemplified by a central penicillin core that contains
fused -lactam and thiazolidine rings Various substituted thiazolidines feature exclusively broad
range of biological activities that warrants a constant interest in preparing new thiazolidines and
studying their properties
Addition of thiourea derivatives to maleic anhydride or maleimides is used to get a rich
functionalized thiazolidinylacetic acid framework This reactions is classical but at the same time
many questions concerning regioselectivity in case of unsymmetric thioureas remained unclear and
there were problems to be solved Some controversial data and surprising results can be found in the
literature and therefore we decided to thoroughly investigate factors governing the regioselectivity
of this process
We have shown that addition of N-aryl-Nrsquo-ethyl(or methyl)thioureas to N-arylmaleimides proceeds
regioselectively providing 2-(3-ethyl(methyl)-2-arylimino-4-oxo-13-thiazolidin-5-yl)-N-
arylacetamides in good yields It is applicable for a wide range of substituents in aromatic rings and
the product selectivity does not depend on the solvent used A remarkable dependence of the
reaction regioselectivity on the solvent polarity was revealed with more sterically hindered alkyl
thioureas In nonpolar benzene 3-alkyl-2-arylimino-4-oxo-13-thiazolidines are formed
preferentially whereas in polar isopropyl alcohol and acetonitrile the reaction regioselectivity
changes in favor of 2-alkylimino-3-aryl-4-oxo-13-thiazolidines In the case of the most bulky
N-tert-butyl-Nrsquo-phenylthiourea the isomer with exo-cyclic position of an alkyl group is formed
exclusively At the same time addition of sterically hindered N-alkyl-Nrsquo-arylthioureas to maleic
anhydride leads only to 3-alkyl-2-arylimino-4-oxo-13-thiazolidinylacetic acids independent of the
solvent used We have unambiguously established the structures of all obtained thiazolidines (some
of them using X-ray data) and demonstrated the utility of the 15
N-1H HMBC spectroscopy for their
unequivocal assignment
Authors thank the Russian Scientific Fund for a research grant no 14-13-00126
232
P121
MECHANISTIC STUDY OF Cu2O AND CuO-CATALYZED CndashS CROSS
COUPLING REACTION
YS Panova1 VP Ananikov
2
1 - Saint-Petersburg State University Institute of Chemistry Russia Petrodvorets Universitetsky
pr 26
2 - N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Russia Moscow
Leninsky pr 47
C-S cross-coupling is a valuable synthetic tool to prepare a diversity of sulfur derivatives with high
yields [12] In spite of various synthetic applications the mechanism of C-S cross-coupling was not
clearly resolved Catalytic reactions mediated with CuO and Cu2O nanoparticles represent a
substantial challenge in this regard
In order to have a better insight of the reaction pathways detailed FE-SEM ESI-MS and NMR
studies were carried out Ligand-free copper oxides (I II)-catalyzed reactions of thiophenol with 4-
iodotoluene were chosen as a model reaction The role of copper centers on the surface of the
nanoparticles and in solution was studied and compared to reported in the literature reaction
pathways
It is interesting to note DFT calculations revealed that strongly polar solvent (like DMSO)
facilitates the formation of the anionic active species [Cu(SPh)2]- [3] This type of intermediates is
favored for halogen atom transfer mechanism as its activation energy barrier much lower (332
kcalmol) then the activation energy barrier of the most often suggested oxidative addition
mechanism (413 kcalmol) according to theoretical study [3]
Based on calculations and experimental data we will discuss the following catalytic pathways 1)
generation of [Cu(SPh)2]- complex by reaction of thiophenol with the base and copper oxides 2)
iodine atom transfer from 4-iodotoluene to Cu-center to form the [Cu(SPh)I]- intermediate and
phenyl radical 3) attack by phenyl radical at S atom of Ph-thiolate affording the formation of
coupling product It is noteworthy that in the absence a base intermediate [CuI2]- was observed by
ESI-MS analysis
References [1] S Ganesh Babu R Karvembu Tetrahedron Lett 2013 54 1677ndash1680
[2] S-W Cheng M-C Tseng K-H Lii C-R Leec and S-G Shyu Chem Commun 2011 47
5599ndash5601
[3] S-L Zhang and H-J Fan Organometallics 2013 32 4944-4951
Acknowledgment PY acknowledges Saint-Petersburg State University for postdoctoral fellowship
(125015602013)
233
P122
TRANSFORMATIONS OF CYCLIC ORGANIC PEROXIDES IN THE
PRESENCE OF TRANSITION METALS
ZY Pastukhova1 IA Yaremenko
1 LG Bruk
2 AO Terentrsquoev
1
1 - N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences
2 - Lomonosov Moscow State University of Fine Chemical Technologies
Currently organic peroxides are produced by dozens of the largest chemical companies in a large-
tonnage scale Peroxides are the main source of free radicals in chemical practice They are widely
used to initiate radical including chain-radical processes especially in the polymer manufacture In
the past decades the chemistry of organic peroxides has attracted considerable attention from
physicians and pharmacologists due to the detection of these compounds high antimalarial
anthelminthic and antitumor activities
Thermal instability of peroxides because of the presence of weak O-O bonds leads to
decomposition at normal or elevated temperatures Transition metals (Fe Сu Мn Со Сr) and their
salts are effective catalysts of decomposition Usually decomposition of organic peroxides is
nonselective process Decomposition reactions are not limited by the only homolytic decomposition
of O-O bond resulting in a complex product mixture is generated
In our work we found the selective transformations of cyclic organic peroxides in the presence of
transition metals (Scheme 1)
Scheme 1 Transformations of Cyclic Organic Peroxides
Mn+
OO
O
OO
OO
O O
This work is supported by RFBR 14-03-00237
Terentrsquoev AO Yaremenko IA Chernyshev VV Dembitsky VM Nikishin GI J Org Chem
2012 77 1833-1842
Terentev AO Yaremenko IA Vil VA Dembitsky VM Nikishin GI Synthesis 2013 45 (2)
246-250
Ingram K Yaremenko IA Krylov IB Hofer L Terentev AO and Keiser J J Med Chem
2012 55 (20) 8700-8711
234
P123
ENANTIOSELECTIVE HYDROLYSIS OF 3-HYDROXY-14-
BENZODIAZEPIN-2-ONE ESTERS BY PIG LIVER MICROSOMES
VI Pavlovsky1 EA Shesterenko
1 II Romanovska
1 OV Sevastyanov
1 TA Yurpalova
1 SA
Andronati1 VCh Kravtsov
2
1 - AV Bogatsky Physico-chemical Institute National Academy of Sciences of
Ukraine Lustdorfska dor 86 Odessa Ukraine
2 - Institute of Applied Physics Academy of Sciences of Moldova Chisinau Republic
of Moldova
The configuration of chiral biologically active compounds plays an important role in processes of their
biotransformation and binding with biomembranes Methods of asymmetric synthesis and resolution of
enantiomers are fraught to difficulties thus development of economical preparative biotechnological
methods of enantiomers resolution is prospective
Carboxylesterase (EC 3111) is the most studied enzyme which catalyze the enantioselective hydrolysis of
a wide range of acyclic carbocyclic and heterocyclic compounds But the number of publications devoted to
the enantioselective hydrolysis of benzodiazepine derivatives which clinical effects include anxiolytic
anticonvulsant and hypnotic effects muscle relaxation is quite limited
The aim of the present work was the development of a method of the enantioselective hydrolysis of 3-
hydroxy-14-benzodiazepin-2-one esters by pig liver microsomes and investigation of S-enantiomers binding
affinity for central benzodiazepine receptors
Microsomal fraction was isolated by the low speed centrifugation method in the presence of Ca2+
ions
Protein yield was 380 mgg of liver tissue and esterase activity was 1725 Umg protein
The method of enantioselective hydrolysis of 1-unsubstituted-(1) 1-methyl-(2) 1-ethyl-(3) 3-acetoxy-7-
bromo-5-phenyl-12-dihydro-3H-14-benzodiazepin-2-ones using pig liver microsomal fraction was
developed (esterase activity 130- Ucm3 pH 70 t 37 ordmC τ 25 h DMSO concentration 40 (vv))
Enantiomers of 3-hydroxy-14-benzodiazepin-2-one esters were purified by silica gel column
chromatography Enantiomeric excesses of substrates (ees) were determined by HPLC using Shimadzu LC-
8A pump with a chiral column ChiraDex It was shown that the products of the reaction ndash 1-unsubstituted-
(4) 1-methyl-(5) 1-ethyl-3-hydroxy-7-bromo-5-phenyl-12-dihydro-3H-14-benzodiazepin-2-ones (6)
underwent racemization during hydrolysis and subsequent isolation what is consistent with the literature
data [1]
The S-enantiomers of three substrates 1S-3S were obtained with ees gt97 and yields 44-49 their
absolute configurations were determined by X-ray crystallography (fig)
1S
2S
3S(a)
3S(b)
Fig ORTEP view of molecular structure of 1S 2S and two conformers in the structure 3S (a and b)
illustrates their absolute configuration
Values of specific rotation 20
Dof 1S-3S were +1169ordm +1953ordm +1938ordm (c = 10 CHCl3) respectively
With a help of the radioligand binding methods affinity of S-enantiomers 1S-3S and racemates 1-3 for the
CBR of rat brain was determined and values of IC50 were evaluated It was shown that the S-enantiomers
1S-3S are 14-21 times more potent ligands of CBR than the corresponding racemates 1-3
References 1 Oswald P Desmet K Sandra P et al 2002 Determination of the enantiomerization energy barrier of some 3-
hydroxy-14-benzodiazepine drugs by supercritical fluid chromatography J Chromatogr B 779 283ndash295
235
P124
A SIMPLE TECHNIQUE FOR PRODUCING PALLADIUM
NANOPARTICLES ON CARBON SUPPORT AS CATALYST FOR
CROSS-COUPLING REACTIONS
EO Pentsak VP Ananikov
ND Zelinsky Institute of Organic Chemistry RAS Moscow Russia
Recently much attention has been paid to carbon materials modified by metal nanoparticles due to
increasing interest in using of such systems in catalysis material science optics and electronics
Successful application of palladium nanoparticles supported on carbon materials was facilitated
many organic synthesis procedures Efficiency and selectivity of these catalysts was determined by
such characteristics as particles size the uniformity of their distribution on the support surface and
the range of particle size distribution
We have previously shown that the labile behavior in solution and the tendency to form palladium
clusters are inherent in Pd2dba3 complex [1]
Thus we were able to cover carbon material by
nanoparticles with optimum sizes and high monodispersity under mild conditions without the need
of stabilizers and reducing agents using easily available Pd2dba3 complex as a precursor of
palladium
In this study we found that the variation of temperature and concentration of solution allowed
tuning of coverage density of the supported nanoparticles as well as control of diameter of the
nanoparticles from 2 to 15 nm This procedure was found scalable and well reproducible
Dispersion values of the nanoparticles sizes usually did not exceed 1-2 nm Kinetics of the process
was investigated by nuclear magnetic resonance spectroscopy NMR and scanning electron
microscopy (FE-SEM) Study of deposition process by FE-SEM showed that the average particles
size was stabilized quickly during the coating process The particles size depended on the
conditions of the process while the increase of the coating density occurred gradually until
complete consumption of the Pd precursor
The catalytic activity of prepared palladium nanoparticles supported on graphite has been studied
utilizing model Suzuki and Heck reactions The catalyst prepared by our method showed high
efficiency for this type of reactions 100 conversion of the Heck and Suzuki reactions was reached
only in a few hours at low catalyst loadings (02-05 mol )
[1] Zalesskiy S S Ananikov V P Organometallics 2012 V 31 P 2302ndash2309
236
P125
SELECTIVE CLEAVAGE OF GLYCOSIDIC LINKAGES USING
SOLVOLYSIS WITH ANHYDROUS TRIFLUOROACETIC ACID
SN Senchenkova AV Perepelov AV Filatov AS Shashkov YA Knirel
NDZelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
A common approach in structural studies of polysaccharides is the selective cleavage of glycosidic
linkages to give oligosaccharide fragments which usually show better-resolved NMR spectra than
the parent polymer and are readily amenable to MS analysis One of the methods useful for this
purpose is solvolysis with strong acids For instance solvolysis with anhydrous HF has been used in
structural analysis of carbohydrates since early 1980s and later trifluoromethanesulfonic (triflic)
acid was introduced However these reagents have some disadvantages eg HF handling requires
special equipment triflic acid is expensive and both are highly hazardous In search for a better
solvolytic agent we tested anhydrous CF3CO2H in selective cleavage O-polysaccharides of
medically important bacteria Escherichia coli and Enterobacter cloacae and found it to be useful
and convenient CF3CO2H split selectively the α1rarr2- and α1rarr3-rhamno- and -fuco-pyranosidic
linkages as well as the HexpNAc-(1rarr4)-Manp linkage whereas other linkages were not affected
Below are structures of the cleaved O-polysaccharides (O68 at 50degC for 16 h all others at 40degC for
5 h) with the glycosidic linkages sensitive to CF3CO2H shown in rectangles
237
P126
СROSS-COUPLING OF TEREPHTHALONITRILE DIANION AND
AROMATIC NITRILE RESULTING IN SUBSTITUTED DICYANOBIARYLS
RYu Peshkov1 EV Panteleeva
1 VD Shteingarts
2
1 - Novosibirsk State University Novosibirsk Russia
2 - NN Vorozhtsov Novosibirsk Institute of Organic Chemistry Novosibirsk Russia
Cyanobiaryls have a wide area of practical utilization in technology (polymers semiconductors
OLED) as well as in medicine [1] Modern approaches to their synthesis are based on manifold
cross-coupling reactions of preactivated arenes catalyzed by transition metals We suggest a concise
and inexpensive non-catalytic approach applying terephthalonitrile dianion 1 as cyanoarylating
reagent for neutral aromatic nitriles It was found that 1 generated by terephthalonitrile reduction
with alkali metal in liquid ammonia undergoes cross-coupling with benzonitrile as well as 2- and 3-
cyanobiphenyls providing 44`-dicyanobiphenyl and dicyanoterphenyls [2] Present work is aimed
on broadening the scope of neutral substrates applicable for such type of cross-coupling and study
of its mechanism by revealing electronic and structural factors governing regioselectivity and
efficiency of the reaction For the purpose we varied the nature of substrate by introduction of an
extra substituent into benzonitrile (Me MeO F Cl Br) as well as by alteration of aromatic moiety
(cyanonaphthalenes 9-cyanoanthracene 4-cyanopyridine) Besides nitriles electron-deficient
arenes ethylbenzoate 3-methylbenzophenone and nitrobenzene were tested Also experimental and
quantum-chemical modeling of possible reaction pathways were performed We found out that
benzonitriles substituted with o- m-Me -MeO and -F both cyanonaphthalenes and 9-
cyanoanthracene undergo coupling with 1 providing subsequent cyanobiaryls (scheme) Towards all
other substrates 1 acts as reducing reagent The regularities revealed are interpreted in terms of the
reaction scheme with the intermediacy of the charge-transfer complex 2 between 1 and cyanoarene
[2] which further transforms into dimeric dianion 3 either by heterolytic pathway or by successive
single electron transfer and recombination of primary generated radical anions Subsequent
decyanation of 3 forms long-living monoanion 4 capable to be converted into cyanobiarylic product
either through oxidation or alkylation
CN
CN
2-
CN CN
CN
2-
CN CN
CN
CN
+
primary RA-pairCTC
CN
CN
CN
-CN-
CN
CN
CNNC
CN
AlkBr
NC Alk
CN
Alk
-H+
-CN-
[O]
X X X
X X
X X
X
ETin-cage
recombination
heterolytic pathway (SNAr)-Br-
2M+CN
2-
CNNH3
M Li Na K
ArX
CN CNCN CNCN
F
F
F FF
FFF
CN
Bu
CN CN
F CN
CN
CN
CN
CN
CN
CN
CNCN
CNX
CNNC
X
X
cyanobiaryleyield 14-90
X
X H 2- 3-CH3 -OCH3 -F
ArX
CN
CN
X
CN
CN
F F
12
3 4
Bu
CNCN
CN
CN
The financial support of the CMSD of RAS (the project No 26) is acknowledged
[1] Corbet J-P Mignani G Chem Rev 2006 106 2651
[2] a) Panteleeva EV et al Eur J Org Chem 2005 2558 b) Panteleeva EV et al
ARKIVOC 2011 viii 123
238
P127
REARRANGEMENT OF CYCLIC 9-MEMBERS Si-PEROXIDES
RA Pototskiy1 RA Novikov
2 AO Terentev
1 GI Nikishin
1 AV Arzumanyan
1
1 - N D Zelinsky Institute of Organic Chemistry Laboratory for Studies of Homolytic Reactions
Moscow Russia
2 - N D Zelinsky Institute of Organic Chemistry Laboratory of Carbene Chemistry and Small-
Sized Cyclic Compounds Moscow Russia
Among organic peroxides compounds with SiOO moiety are less known than their carbon
analogues As the result there are few examples of reaction of silicon containing peroxides in
literature
In the previous works we reported about successful synthesis of different silicon containing cyclic
peroxides [12]
Now we focused on investigation of treatment of such compounds with different reducers and
Lewis acids (LA)
It has been shown that treatment of the cyclic Si-peroxides with different
reducers leads to contraction of peroxide cycle on two oxygen atoms Notably
each peroxide group lost one oxygen atom giving earlier unknown silyl-
protecting diols Reaction was carried out in diethyl ether medium at ambient
temperature in the presence of 3-fold access of a reducer The best results were
reached with triphenylphosphine Yield of products were 60 to 75 depending
on structure of starting substance Such products may be used as building blocks
bin different bioactive compounds
Treatment of bis-sililperoxides under LA action was studied The reaction was carried out in
different reaction media with 2-fold excess of LA (SnCl4 TiCl4 AlCl3) It has been established that
the way of reaction depends on nature LA catalyst For example formation of lactones yield of 80 ndash
95 was observed (Bayer-Villiger-like reaction) in the presence of SnCl4 In case of TiCl4 the
combination of a regrouping and formation of an appropriate ketone was observed with AlCl3
reaction did not flow past
Summary in this work chemical reactions of cyclic Si-peroxide compounds have been investigated
Organic silicon peroxide compounds can enter various reactions leading to formation of lactones
diols with a trialkylsilyl group depending on reaction conditions that point to their high synthetic
potential
References
[1] Arzumanyan AV Terentrsquoev AO Nikishin GI etal Organometallics 2014 33 2230-2246
[2] Platonov MM Terentrsquoev AO Nikishin GI etal J Org Chem 2008 73 3169-3174
R R
S i
O
S i
O
O O
239
P128
EFFICIENT ONE-POT SYNTHESIS OF DIVERSE BENZO[C[CHROMENE-
6-ONES BY BASE-PROMOTED CASCADE REACTIONS
TN Poudel YR Lee
School of Chemical Engineering Yeungnam University Gyeongsan 712-749 Republic of Korea
Molecules bearing benzo[c]chromen-6-one and its derivatives are extensively distributed in nature1
Some of these molecules exhibit biologically and pharmacologically important antitumor and
antibiotic activities2 promote endothelial cell proliferation and inhibit oestrogene receptor growth
activities3 Due to the importance of these biological and pharmacological activities several
synthetic methods have been devised to produce benzo[c]chromen-6-one derivatives Of these
methods the most useful method involves a Suzuki-Miyaura cross-coupling reaction followed by
metal or Lewis acid mediated lactonization of ester and methoxy groups4
Recently a new reaction
involving a microwave-assisted Diels-Alder reaction betwee 4-cyanocoumarin and 1-oxygenated
dienes followed by elimination and aromatization with a strong base was also described5 However
these synthetic approaches included two-step reactions and required purification of the intermediate
In addition the starting materials used for these transformations were synthesized from
corresponding materials in two or more steps Thus a mild general and efficient one-pot synthetic
route for benzo[c]chromen-6-one derivatives using inexpensive catalysts and reagents is still in
demand especially a route that allows minimization of the steps and access to diverse products
We present herein a novel one-pot synthesis of a variety of benzo[c]chromen-6-one derivatives
using Cs2CO3-promoted reactions of substituted 2-hydroxychalcones and β-ketoesters These
reactions involved cascade Michael addition intramolecular aldol oxidative aromatization
lactonization and provided an efficient synthetic route for the production of biologically interesting
novel benzo[c]chromen-6-one molecules bearing several different substituents on benzene rings As
an application of this methodology several synthesized benzo[c]chromen-6-ones were transformed
into highly functionalized novel terphenyls
References
1 (a) Ya L Garazd A S Ogorodniichuk M M Garazd andV P Khilya Chem Nat Compd
2002 38 424 (b) K Ishiguro M Yamaki M Kashihara S Takagi and K Isoi
Phytochemistry1990 29 1010 (c) H Abe K Nishioka S Takeda M Arai Y Takeuchi and
T Harayama Tetrahedron Lett200546 3197
2 (a) T Hosoya E Takashiro T Matsumoto and K Suzuki J Am Chem Soc1994 116
1004(b) C A James and V Snieckus Tetrahedron Lett1997 38 8149
3 (a) J M Schmidt G B Tremblay M Page J Mercure M Feher R Dunn-Dufault M G Peter
and P R Redden J Med Chem 2003 46 1289(b) J Pandey A K Jha and K Hajela
Bioorg Med Chem2004 12 2239
4 (a) Q J Zhou K Worm and R E Dolle J Org Chem2004 69 5147 (b) G J Kemperman
B Ter Horst D Van de Goor T Roeters J Bergwerff R Van der Eem and J BastenEur J
Org Chem2006 14 3169
5 M EJung and D A Allen Org Lett 2009 11 757
240
P129
PRACTICAL SYNTHESIS OF 124-THIADIAZOLES VIA`
COPPER-MEDIATED HOMO-COUPLING OF THIOAMIDES
Y-D Sun C-R Qi H-F Jiang
South China University of Technology College of Chemistry amp Chemical Engineering Guangzhou
P R China
Thiadiazoles are regarded as an important class of five-membered heterocycles for many bioactive
molecules One general method for the preparation of 124-thiadiazoles containing the same groups
in 3- and 5-positions was oxidative dimerization of the corresponding thioamides using oxidizing
agents One the other hand the transition metal-mediated oxidative transformations to construct
heterocycles have attracted great interest over the past decade In particular copper salts have been
successfully applied in the formation of C-hetero or hetero-hetero bonds which exhibit great
potential for the construction of various heterocycles On the basis of our recent developed Cu-
catalyzed method for synthesis of heterocycles1-5
and increasing interest of oxidative cross-coupling
reactions of two nucleophiles herein we disclose a novel method for 35-disubstituted 124-
thiadiazoles via copper(II)-mediated homo-coupling of thioamides involving C-N and N-S bond
formations (Scheme 1)
Scheme 1 Synthesis of 124-thiadiazoles
References
1 Huang L Jiang H Qi C Liu X J Am Chem Soc 2010 132 17652
2 Li X Huang L Chen H Wu W Huang H Jiang H Chem Sci 2012 3 3463
3 Gao Y Yin M Wu W Huang H Jiang H Adv Synth Catal 2013 355 2263
4 Zeng W Wu W Jiang H Huang L Sun Y Chen Z Li X Chem Commun 2013 49
6611
5 Sun Y Jiang H Wu W Zeng W Wu X Org Lett 2013 15 1598
241
P130
HIGHLY EFFICIENT SYNTHESIS OF TERTIARY α-HYDROXY KETONES
VIA CO2-PROMOTED REGIOSELECTIVE HYDRATION OF
PROPARGYLIC ALCOHOLS
H-T He C-R Qi H-F Jiang
South China University of Technology College of Chemistry amp Chemical Engineering Guangzhou
P R China
-Hydroxy ketones have attracted tremendous interest in biologically active natural product
research and synthetic chemistry However few of methodologies could be applicable for efficient
hydration of propargylic alcohols to form -hydroxy ketones except the Kucherov reaction using
mercury(II) salts as catalysts A wide range of transition metals including Pd Pt Fe Au Ag Ir and
Ru have been investigated for the hydration of alkynes however these catalytic systems either
showed low activity or led to side reactions such as Meyer-Schuster and Rupe rearrangements
Therefore the development of novel processes for the hydration of propargylic alcohols to produce
-hydroxy ketones with high efficiency is highly desirable
Using CO2 as the feedstock a great deal of work in many different fields has been undertaken to
produce cyclic carbonates In our previous work1 2
we found that secondary amine was able to
attack the carbonyl group of the α-methylene cyclic carbonate to give the ring-opening product
Recently we set out to study whether water was capable to proceed the nucleophilic attack instead
of the secondary amines to furnish useful -hydroxy ketone derivatives (Scheme 1)
Scheme 1
References
[1] Qi C Jiang H Green Chem 2007 9 1284
[2] Qi C Huang L Jiang H Synthesis 2010 9 1433
242
P131
UNEXPECTED DIRECT CONVERSION OF FUSED 125-
SELENADIAZOLES INTO 125-THIADIAZOLES
LS Konstantinova EA Knyazeva OA Rakitin
ND Zelinsky Institute of Organic Chemistry RAS
Fused 125-thiadiazoles have attracted much attention because of their interesting chemical
properties and various possibilities for use as antibacterial and antiviral agents agrochemicals and
as π-type building blocks for organic electronics particularly for both low- and high-molecular
organic light-emitting diodes (OLEDs)1 Recently 125-thiadiazole derivatives were recognized as
efficient electron acceptors and successfully used in the preparation of radical-anion salts revealing
antiferromagnetic exchange interactions in their spin systems and conductive charge-transfer
complexes2 Although methods for the preparation of fused 125-thiadiazoles are numerous and
well elaborated there is still a lack of syntheses of derivatives containing electron-deficient
heterocycles
We have found that treatment of 125-selenadiazoles fused with nitrogen heterocycles such as
piperazine and thia(selena)diazole with S2Cl2 in DMF gave unexpectedly corresponding 125-
thiadiazoles in high yields This is the first case of direct substitution of the selenium to sulfur atom
in 125-selenadiazoles The driving force of this reaction is the precipitation of elemental selenium
which was isolated from the reaction mixtures in practically quantitative yield
We gratefully acknowledge financial support from the Russian Foundation for Basic Research
(Project 13-03-00072) from the Presidium of the Russian Academy of Sciences (Programme No 8)
and from the Leverhulme Trust (Project IN-2012-094)
1 Todres ZV Chalcogenadiazoles Chemistry and Applications CRC PressTaylor amp Francis
Boca Raton 2012 290 pp
2 N A Semenov N A Pushkarevsky E A Suturina E A Chulanova N V Kuratieva A S
Bogomyakov I G Irtegova N V Vasilieva L S Konstantinova N P Gritsan O A Rakitin
V I Ovcharenko S N Konchenko A V Zibarev Inorg Chem 2013 52 6654
243
P132
ACTIVATION OF HYDROPEROXIDES BY TETRAALKYLAMMONIUM
BROMIDES
EV Raksha1 YuV Berestneva
1 NA Turovskij
1 MYu Zubritskij
2
1 - Donetsk National University Physical chemistry Department Donetsk Ukraine
2 - LM Litvinenko Institute of Physical Organic and Coal Chemistry National Academy of
Sciences of Ukraine Donetsk Ukraine
The investigation of supramolecular catalysis of organic peroxides decomposition is the actual
direction in the development of peroxide initiators chemistry There are a wide range of catalytic
systems for the radical decomposition of hydroperoxides and quaternary ammonium salts are
occupied an important place among of them The key feature of supramolecular hydroperoxides
decomposition in the presence of Alk4NBr is the complex formation between the reactants [1]
Systematic kinetic investigations of the interaction between hydroperoxides and Alk4NBr have been
carried out [1] Activation energies of the hydroperoxides thermolysis and catalytic decomposition
have shown to be change simbatically Kinetic parameters of the hydroperoxide-catalyst complex
decomposition have been determined Lowering of the activation barrier for the complex-bonded
hydroperoxide decomposition as compared with its thermolysis in acetonitrile is 40 kJmiddotmol-1
The interaction of tert-butyl as well as 113-trimethyl-3-(4-methylphenyl)butyl hydroperoxides
with tetraalkylammonium bromides (Alk4NBr) has been studied by NMR spectroscopy The
complexation between reactants was observed by relative change of the chemical shifts in the NMR 1H spectra The complex formation between the hydroperoxide molecule and corresponded
quaternary ammonium salt has been proved Thermodynamic parameters of complex formation
have been determined
The equilibrium constants of complex formation (KС) between tert-butyl hydroperoxide and
Alk4NBr have been determined both by NMR 1H and
13C spectroscopy The values of the ΔcompH
for the hydroperoxide complex with investigated salts are negative and lie are within -20 divide -9
kJmiddotmol-1
7 in CDCl3 solution that corresponds to the formation of weak hydrogen bonds Similar
effect has been observed in CD3CN solution for the hydroperoxide-Alk4NBr systems
The equilibrium constant values as well as complexation enthalpies decrease with intrinsic
tetraalkylammonium cation volume increasing and this effect is observed over the temperature
range 297-313 K Complexation enthalpies defined by kinetic and NMR spectroscopy methods
coincide
The structural model has been proposed for the complex of hydroperoxides with Alk4NBr It
includes the hydroperoxide molecule salt cation and anion as well as solvent molecule Structural
reorganization of the hydroperoxide fragment is the key factor of the chemical hydroperoxide
activation in the presence of Alk4NBr
[1] NА Тurovskij EV Raksha YuV Berestneva et al in Polymer Products and Chemical
Processes Techniques Analysis and Applications Editors RA Pethrick EM Pearce GE
Zaikov ndash Toronto New Jersey Apple Academic Press 2013 ndash 323 p ndash P 269-284
[2] NА Тurovskij YuV Berestneva EV Raksha et al Polymers Research Journal ndash 2014 ndash
Vol 8 No 2 ndash P 85 ndash 90
[3] NА Тurovskij EV Raksha YuV Berestneva MYu Zubritskij Russian Journal of General
Chemistry ndash 2014 ndash Vol 84 Iss 1 - P 16-17
[4] NА Тurovskij YuV Berestneva EV Raksha et al Monatshefte fuumlr Chemie - Chemical
Monthly DOI 101007s00706-014-1234-5
244
P133
THE AZA-COPE-MANNICH REACTION APPLICATION TO THE
SYNTHESIS OF UNNATURAL L-ALANINE DERIVATIVES
NK Ratmanova DS Belov IA Andreev AV Kurkin
Lomonosov Moscow State University Department of Chemistry Moscow Russia
Unnatural amino acids represent a nearly infinite array of diverse structural elements for the
development of new leads in peptidic and non-peptidic compounds Due to their seemingly
unlimited structural diversity and functional versatility they are widely used as chiral building
blocks and molecular scaffolds in constructing combinatorial libraries
Herein we report the synthesis of the enantiopure unnatural L-alanine derived trans-
octahydrocyclohepta[b]pyrroles 5a and 5b via the aza-Cope-Mannich reaction (Scheme 1) Epoxide
2 (the source of chirality) was prepared according to the literature procedures from commercially
available alcohol 1 applying Shi epoxidation protocol1 The LiClO4-meditated epoxide ring-opening
of 2 with L-alanine ethyl ester gave the diastereomeric mixture of amino ethanols 3a and 3b After
the chromatographic separation the compounds 3a and 3b were obtained as single isomers with
high enantiomeric purity (ee = 99 and 86 respectively chiral HPLC) The hydrogenation of 3a
and 3b on the Lindlar catalyst gave desired alkenes 4a and 4b and unexpected side products (S)ndash
and (R)ndashethyl 2ndash(4567ndashtetrahydrondash1Hndashindolndash1ndashyl)propanoates Finally carrying out the aza-
Cope-Mannich reaction under previously optimized conditions2 gave the target enantiopure
products 5a and 5b without epimerization
Scheme 1 Synthesis of target compounds 5a and 5b
As a result two diastereomeric unnatural L-alanine analogues 5a and 5b were synthesized in 5
steps from commercially available materials The study showed that conditions of the aza-Cope-
Mannich reaction are mild enough to be applied in the complex settings for example to the
synthesis of molecules with several stereocenters which are prone to racemization3
This study was supported by the Russian Foundation for Basic Research (RFBR) Russia (Projects
No 14-03-31685 14-03-31709 14-03-01114)
References
1 Wang Z-X Cao G-A Shi Y J Org Chem 1999 64 7646ndash7650
2 Belov D S Lukyanenko E R Kurkin A V Yurovskaya M A J Org Chem 2012 77
10125ndash10134
3 Ratmanova N K Belov D C Andreev I A Kurkin A V Tetrahedron Asymmetry 2014
25 468ndash472
245
P134
MECHANISTIC STUDIES OF PALLADIUM-MEDIATED ALKYNE
INSERTION REACTION USING ELECTROSPRAY IONIZATION TANDEM
MASS SPECTROMETRY
KS Rodygin1 LL Khemchyan
2 VP Ananikov
2
1 - Saint Petersburg State University Institute of Chemistry Stary Petergof Russia
2 - N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
Rapid development of transition metal catalysis allows rational design of a new methodology to
carry out three-component coupling To achieve this aim challenging question concerning
mechanistic features of insertion reaction should be resolved[1]
Oxidative addition of an aryl halide to Pd in Pd(PPh3)4 (a common source of Pd in cross-coupling
reactions) is the first step in the catalytic cycle Addition of an alkyne to the mixture containing
Pd(PPh3)2ArX results in the formation of another intermediate Pd(Ar)(PPh3)2(alkyne)X The
intermediate containing the alkyne-unit has three possibilities to evolve π-complex acetylide or
vinyl complex (insertion product)
For development of the present project it was important to reveal the nature of transition metal
intermediates and their role in the catalytic cycle in order to improve selectivity and scope of
three-component coupling reaction The questions of key importance in this regard (see Scheme)
how facile is the insertion reaction And what types of complexes ndash π-complex acetylide or vinyl
complex ndash are formed
Few important features of the studied system deserve a note Oxidative addition proceeds with
formation of Pd complex the corresponded ion was detected as [Pd(PPh3)2Ph]+ The elimination of
PPh3-containing species is typical and expected under these conditions More interesting series of
alkyne insertions into Pd-C bond starting from initial complex lead to the formation of
Pd-containing vinyl complexes Reductive elimination results in formation of corresponded
substituted alkenes dienes triene and tetraene Note formation of these Pd-free olefinic species
provides an evidence for the fact of alkyne insertion into Pd-C bonds
On the next stage ESI-(+MSMS) experiment via collision-induced dissociation (CID) was
performed The detected fragment ions serve as an additional evidence for the investigated alkyne
insertion step In the present study we were able to distinguish π-complex and insertion intermediate
using ESI-(MSMS) experiment
KR gratefully acknowledges Saint Petersburg State University for a postdoctoral fellowship (
125015602013)
References
[1] Hydrofunctionalization VPAnanikov MTanaka (Eds) Springer 2013 Heidelberg ISBN
978-3-642-33734-5
246
P135
FACILE AND EFFICIENT SYNTHESIS 2-AMINO-4H-CHROMENES VIA
SOLVENT-FREE CASCADE ASSEMBLING OF SALICYLALDEHYDES
AND CYANOACETATES
FV Ryzhkov RF Nasybullin MN Elinson
N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences 119991 Moscow
Russian Federation
2-Amino-4H-chromenes (or 2-amino-4H-benzo[b]pyranes) are of particular interest as they belong
to privileged medicinal scaffolds serving for generation of small-molecule ligands with highly
pronounced spasmolitic- diuretic- anticoagulant- and antianaphylactic activities [1] The current
interest in 2-amino-4H-chromenes bearing nitrile functionality arises from their potential
application in the treatment of human inflammatory TNFα-mediated diseases such as rheumatoid
and psoriatic arthritis and in cancer therapy [2]
The development of solvent-free organic synthesis has become an important research area This is
not only due to the need for the more efficient and less labour-intense methodologies for the
synthesis of organic compounds but also because of the increasing importance of the
environmental considerations in chemistry The elimination of volatile organic solvents in organic
synthesis is also the most important goal in lsquogreen chemistryrsquo
We were prompted to use a convenient and facile solvent-free cascade methodology for the
synthesis of 2-amino-4H-chromene scaffold from salicylaldehydes and cyanoacetates We have
found that potassium fluoride as catalyst can produce under solvent-free mild conditions a fast and
selective cascade trasformation of salicylaldehydes and cyanoacatates into substituted at ambient
temperature 2-amino-4H-chromenes chromenes in 88ndash98 yields
The catalytic procedure utilizes simple equipment it is easily carried out and is valuable from the
viewpoint of environmentally benign diversity-oriented large-scale processes This efficient
potassium fluoride catalyzed solvent-free approach to substituted 2-amino-4H-chromenes represents
a new synthetic concept for cascade reactions and allows for the combination of the synthetic
virtues of conventional cascade processes with ecological benefits and convenience of solvent-free
procedure 1 H Aryapour M Mahdavi SR Mohebbi Frch Pharm Res 2012 35 9 1573-1582
2 J Skommer D Wlodkowic M Matto MEray J Pelkonen Leukemia Res 2006 30 322-333
247
P136
A NEW 3D CHEMICAL FORMULAS FOR ANALYZING OF
GEOMETRICAL STRUCTURES OF ACTIVE BIOMOLECULES IN
laquoSTRUCTURE-ACTIVITYraquo PROBLEM
EA Smolenskii AN Ryzhov PO Guskov IV Chuvaeva
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
We suggest a new way (ldquothe method of trianglesrdquo) to describe 3D molecule structures and solid surfaces with
account their spatial geometry making the difference between stereo and conformational isomers The new
formulas allow using well-known procedures of the ldquostructure-propertyrdquo and ldquostructure-activityrdquo problems for
large molecules Furthermore the method clears the novel ways of circumscribing solid surfaces and in
ldquostructure-catalytic activityrdquo problems The approach is based on taking into account every of the spatial-
orientated atom triples i j k designating triangle Let us to consider vertex i of the triangle and vectors
jiijVVV
kiik
VVV
being the entries of the i-row of the Matrix of Geometrical Distances (MGD) And
now we proceed to description in terms of the triangles matrix
jkij
jkij
ijkjkijijkijkijkjkijijkkji
ijk
VV
VVnVVnVV
sin
2
1
2
1
Since a vectors product determines the triangle it automatically means an orientation of the triangle surface in
space There are 3 sets of indexes with the same direction of normal vectors i jk
n and 3 ones in opposite One can
selects internal or external triangles from the triangle matrix by following rule triangle ijk
is external if
m i j k and i j k 0ijk m
n V for triples of atoms placed on one line i jk
n is determined as vector
that is perpendicular to and finished on this line and started from the mass center of molecule
Changing internal triangles in the matrix ijk
by zeros we get the external triangles matrix
ex
ijk
This matrix
contains the same external triangle i j k three times Thus we define geometrical structure of a molecule
Usually a biomolecule activity is defined by small site being complimentary to its natural substrates The site (ldquok-
complexrdquo) is consisted of k inter-oriented triangles Vector m
F of entry numberslm
a for every type of the k-
complex triangles in molecule with number m may be called as ldquo3D chemical formulardquo of this molecule One can
selects the triangles of k-complex considering the matrix (
M
m
k
N m
CM
1
dimension) of entry numbers lm
a for
every type of the k-complex triangles in each compound of the set m
P ( (1 )m M ) of active and non-active
substances Here lm
a ( 1m M 1
(1 )m
M
k
N
m
l C ) is the entry number of k-complex with number l in m -
compound taking into account conformational isomerism M ndash the number of compounds m
N - the number of
triangles in m-compound
M
m
mNN
1
- the general number of triangles in all substances This matrix is based on
3D chemical formulas Here we must using rule any triangle being among type of triangles contained in inactive
substances cannot be contained in k-complex Remaining triangles (approximately they are contained in k-
complex their number as show on example of set of castanospermines tested by anti-HIV activity [GWJ Fleet
et al FEBS Letters 1988 V 237 1-2 P 128-132] as a rule less than number of active compounds) is used
for making of additive scheme for calculating of biological activity
So 3D chemical formulas can be used for describing genes catalyst surfaces proteins and other biomolecules
248
P137
A PROBLEM OF DEFINITION OF CHEMICAL EQUILIBRIUM IN
CONTEMPORARY CHEMISTRY
AN Ryzhov EA Smolenskii PO Guskov MS Molchanova
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
Unfortunately a many definitions of chemical equilibrium of systems exist and are used now In
process of our investigation we find that principle of detailed equilibrium is sufficient but not
necessary condition of chemical equilibrium from the viewpoint of formal kinetics We propose a
new definitions
1 Steady-state chemical system is called chemical system with constant temperature pressure
volume and activities of compounds
2 Equilibrium chemical system is called steady-state and adiabatically isolated system
3 System with detailed equilibrium is called equilibrium system with equilibrium in all
elementary reactions
4 Quasiequilibrium chemical system is open system with time of parameter stabilization been
more less than time of changing of external conditions
Necessary and sufficient condition of chemical equilibrium is equality between sum of velocities of
elementary reactions with getting of some compound and sum of velocities of elementary reactions
with expenses of this compound for all compounds of system
For system with three compounds
A
B C
in the case of detailed equilibrium
(S=[A]+[B]+[C]) A C C B B A A B B C C Ak k k k k k
B A C A
B A C A A B C A B A A CA
Sk k
k k k k k k
A B C B
A B C B BA C B A B BCB
Sk k
k k k k k k
B C A C
B C A C C B A C B C C AC
Sk k
k k k k k k
For this system in the common case of equilibrium
vBA vAB vCA
vAC
vBC
vCB
249
P138
SYNTHESIS STRUCTURE AND THERMAL PROPERTIES OF
PROPYLENE OXIDE CARBON DIOXIDE AND L-LACTIDE
TERPOLYMERS
ZN Nysenko1 EE Said-Galiev
1 YaE Belevtsev
2 SI Daineko
2 MI Buzin
3 GG Nikiforova
4
AM Sakharov1
1 - NDZelinsky Institute of Organic Chemistry of the Russian Academy of Sciences Moscow
Russia
2 - ANNesmeyanov Institute of Organoelement Compounds of Rusian Academy of Sciences
Physical Chemistry Moscow Russia
3 - ANNesmeyanov Institute of Organoelement Compounds of Rusian Academy of Sciences
Academy of sciences Polymer Physics Moscow Russia
4 - ANNesmeyanov Institute of Organoelement Compounds of Rusian Academy of Sciences
Polymer Physics Moscow Russia
Poly(propylene carbonate) (PPC) is a sustainable polymer that undergoes complete ash-free
incineration accompanied by the formation of CO2 and H2O PPC is prepared by copolymerization
of propylene oxide (PO) with CO2 and it exhibits attractive physical and mechanical properties
responsible for its potential practical applications It is known that ester units introduction into a
polymer chain promotes increasing its biodegradability
Copolymers with different L-lactide concentrations were synthesized in the presence of zinc adipate
The combination of 1Н
13С and 2D
1Н-
13СHMBC NMR DSC FT-IR spectroscopy and GPC
study results allows one to assume that copolymerization of СО2 PO and L-lactide yields to
partially crystalline terpolymers composed of propylene carbonate blocks combined with L-lactic
acid blocks and may be depicted by segment II of structure represented onto Scheme
The synthesis of the terpolymers is not aggravated by side reactions No inversion of the
configuration of L-lactide occurs during its addition to the polymer chain and the copolymer
possesses optic activity that depends on the L-lactide concentration in its chain All possible types
of the PO addition (head-to-head head-to-tail and tail-to-tail) where head-to-tail addition
predominates are found in the propylene carbonate blocks L-Lactic acid content increase was
shown to be accompanied with elevation of terpolymers onset degradation temperature values
The research was supported by the Russian Ministry of Education and Science (Contract No
14513110139)
250
P139
SIMPLE PRECURSORS FOR THE REGIOSELECTIVE SYNTHESIS OF
METHYLENE-EXPANDED ANALOGUES OF C-NUCLEOSIDES
VK Brel1 AV Samet
2 LD Konyushkin
2 VV Semenov
2
1 - AN Nesmeyanov Institute of Organoelement Compounds
2 - N D Zelinsky Institute of Organic Chemistry
Nucleosides with heterocyclic base linked to sugar through CndashC bond instead of CndashN attachment in
natural nucleosides attract much attention because of their chemical and enzymatic stability
Compounds with methylene group inserted between the ring oxygen and the carbon atom linked to
the base moiety are considered as ring-expanded (six-membered ring) analogues of nucleosides
(Figure 1 A) Several of these molecules showed potent antiviral and antitumor activity
We have developed the synthesis of C2 chiral derivatives of
dihydrolevoglucosenone 1a 2a and 3ndash7 as simple precursors for
preparation of methylene-expanded C-nucleosides (A) using pyrolysis of
cellulose as a key step followed by hydrogenation of LG and
introduction of vinyl and ethynyl fragments to 2-position
The opening of 16-anhydrohexitols acetal ring could be used for transformation of derivatives 3ndash7
into methylene-expanded C-nucleosides (Figure 1 A)
O
O
O
O
O
OH
CH
O
O OH
CH
O
O
OH
CH2
O
O OH
CH2
O
O OH
O
N R
O
O OH
N
N
N
CH2Ph
++
LG
Cellulose
7 2b
2a
1b
1a
DLG
stainless steel
autoclave
2 PdC (Sibunit)
EtOAc 40o
20 bar 8 h
6
23
15
4
O
O
O
THF 40o 2 h
CH CMgBr CH2 CMgBr
63
48
85
Et2O rt 2 h
38
42
Et2O
-40o 3 h54-75
84
H2O rt 1 h
Cu(OAc)2
PhCH2N3
RC N+
O-
R
3 Ph
4 p-Me-Ph
5 p-F-Ph
6 Ac
O
OH
C
12
34
5
6
H e t
A
F ig u re 1
251
P140
SYNTHESIS AND BIOLOGICAL EVALUATION OF
FURANOALLOCOLCHICINOIDS
ES Schegravina1 YuV Voitovich
1 NS Sitnikov
1 VI Faerman
1 VV Fokin
1 H-G Schmalz
2
S Combes3 D Allegro
4 P Barbier
4 IP Beletskaya
5 EV Svirshchevskaya
6 AYu Fedorov
1
1 - Department of Organic Chemistry Nizhny Novgorod State University Gagarina av 23 Nizhny
Novgorod 603950 Russian Federation
2 - University of Cologne Department of Chemistry Koln Germany
3 - Institut Paoli-Calmettes Aix-Marseille Universite Laboratory of Integrative Structural and
Chemical Biology Marseille France
4 - Aix-Marseille Universit INSERM UMR_S 911 CRO2 F-13005 Marseille France
5 - MVLomonosov Moscow State University Department of Chemistry Moscow Russian
Federation
6 - Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry RAS Moscow Russian Federation
A series of conformationally flexible furan-derived allocolchicinoids was prepared from
commercially available colchicine in good to excellent yields using a three-step reaction sequence1
Compounds containing a hydroxyl group in the pseudo-benzylic position of the furan side chain
exhibited high cytotoxicity toward epithelial and lymphoid cell lines (AsPC-1 HEK293 and Jurkat)
in the nanomolar concentration range
In vivo studies also demonstrated significant activity of compounds bearing a hydroxymethyl
fragment in the α-position of the furan ring against the tumor growth without symptoms of neuro-
toxicity
Acknowledgment
We thank the Russian Foundation for Basic Research (projects 14-03-91342 and 12-03-00214-a)
The Ministry of Education and Science of The Russian Federation (project 46192014K) The
research is partly supported by the grant 02В49210003 of The Ministry of Education and
Science of the Russian Federation to Lobachevsky State University of Nizhni Novgorod
References
1 Voitovich YuV Sсhegravina ES Sitnikov NS Faerman VI Fokin VV Schmalz H-G
Comes S Allegro D Barbier P Beletskaya IP Svirshchevskaya EV Fedorov AYu
Synthesis and biological evaluation of furanoallocolchicinoids J Med Chem 2014 (submitted)
252
P141
TETRAMETHYLENECYCLOOCTANE ndash A BASIS FOR
POLYSPIROCYCLIC SMALL RING ARCHITECTURES
KN Sedenkova EB Averina SG Bakhtin TS Kuznetsova NS Zefirov
Lomonosov Moscow State University Department of Chemistry Moscow Russia
1357-Tetrakis(methylidene)cyclooctane (1 TMCO) ndash a symmetric tetraene with highly reactive
exo-cyclic double bonds ndash represents a promising starting compound for the synthesis of
polyspirocyclic small ring structures including rotanes and heterorotanes Nevertheless up to date
the synthesis of TMCO was mentioned in one short communication without an experimental
procedure [1] We developed a straightforward synthesis of TMCO from commercial adamantane-
13-dicarboxylic acid (2) The key stage of the synthesis is fragmentation of adamantane pattern of
tetrabromide 3 under the treatment with zinc
COOH
COOH
Zn NaI Na2CO3
DMF 60
1 (TMCO)
CH2Br
CH2Br
3
Br
Br2
74
4 steps
TMCO was shown to demonstrate high reactivity toward diazomethane dihalocarbenes and
epoxidizing reagents undergoing multiple cyclopropanations or epoxidations of four double bonds
to yield polyspirocyclic products 4ndash6
[1+2]-cycloaddition
X
XX
X4 X=CH2 80
5a X=CCl2 95
5b X=CBr2 65
5c X=CBrF 50
6 X=O 501
or epoxydation
Stereochemical features of polyspirocyclopropanated compounds 56 have been thoroughly
examined in experimental (NMR) and theoretical (DFT) studies Comprehensive stereochemical
assignment of TMCO adducts with dihalocarbenes and polyspiroepoxy products was achieved
In course of the work we have found that carrying out the fragmentation of adamantane derivative 3
in presence of traces of water leads to the formation of bis(methylidene)bicyclononane 7 The
addition of dihalocarbenes to diene 7 was shown to be stereoselective giving solely the products of
exo-addition to double bonds 8andashc that was by unambiguously proved by RSA for 8a
CH3
Zn NaI Na2CO3
DMFH2O 160oC 253
7
CHX2Y NaOHaq 8a X=Y=Cl 878b X=Y=Br 728c X=Br Y=F 43
CH3
CXY
CXY
TEBA CH2Cl2
In conclusion we elaborated a preparative gram-scale approach to TMCO and obtained a series of
unique polyspirocyclic structures starting from this highly reactive tetraene
We thank the Russian Foundation for Basic Research (Projects 14-03-31989-mol_а 14-03-00469-
a) and Presidium RAS (program 8P) for financial support of this work
[1] Stepanov F N Sukhoverkhov V D Baklan V F Yurchenko A G Zh Org Khim 1970 6
884ndash885 J Org Chem USSR (Engl Transl) 1970 6 278ndash284