ICIQ-INTECAT School...This ICIQ-INTECAT School is made possible through the generous support from...
Transcript of ICIQ-INTECAT School...This ICIQ-INTECAT School is made possible through the generous support from...
ICIQ-INTECAT School
December 11-13, 2018
Hotel Termes de Montbrió, Tarragona
http://www.iciq.org/agenda/iciq-intecat-school/
2
INDEX
Welcome Address - 3
Acknowledgements - 4
Organizing Committee - 5
Speakers - 5
Program - 6
Abstracts Plenary Lectures - 9
Abstracts Invited Lectures - 18
Abstracts Oral Communications - 21
Abstracts Posters - 38
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WELCOME ADDRESS
We wish to welcome all participants to the ICIQ-INTECAT-Winter-School, which is
organized by the Institute of Chemical Research of Catalonia (ICIQ). We have brought together a prestigious group of international speakers that will cover an
exceptionally broad range of topics at the frontier of chemical research, catalysis,
mechanistic insights, physical organic methods as well as ingenious and improved methods for preparing building blocks of synthetic relevance in both pharmaceutical
and academic laboratories. The scientific program of this symposium includes plenary lectures, invited lectures, short oral communications and poster sessions,
and provides ample time for discussions.
We would like to express our deepest gratitude to all participants for their interest,
which has made this School possible.
This ICIQ-INTECAT School is made possible through the generous support from the
Ministerio de Ciencia, Innovación y Universidades, Agencia Estatal de Investigación
through the RedINTECAT Program (Ref: CTQ2016-81923-REDC/AEI).
We wish you all a wonderful time in the Tarragona region!
Rubén Martín (ICIQ Group Leader)
Kilian Muñiz (ICIQ Group Leader)
4
ACKNOWLEDGEMENTS
Institut Català d’Investigació Química (ICIQ)
Ministerio de Ciencia, Innovación y Universidades, Agencia Estatal de Investigación
(RedINTECAT Ref: CTQ2016-81923-REDC/AEI)
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COMMITTEES
Organising Committee
Kilian Muñiz
Rubén Martín
Organising Manager
Judit Martínez
SPEAKERS
Plenary Lecturers
Prof. Dr. Peter R. Schreiner
Institut für Organische Chemie, Germany
Prof. Timothy Noël
Eindhoven University of Technology, The Netherlands
Prof. Dr. Philippe Renaud
Universität Bern, Switzerland
Prof. Keary M. Engle
The Scripps Research Institute, USA
Invited Lecturers
Prof. José M. González
Universidad de Oviedo, Spain
Prof. J. C (Chris) Slootweg
Universiteit van Amsterdam, The Netherlands
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PROGRAM
Tuesday, 11th December
14:00 – 14:30: Start & Registration
Chaiperson: Eric Cots
14:30 – 15:45: Plenary Lecture 1 - Prof. Dr. Peter R. Schreiner Tunneling Control of Chemical Reactions
15:45 – 17:00: Oral Communications
15:45 – 16:00: Oral Communication 1 – Prof. Antoni Llobet New Energy Conversion Schemes: A Molecular Approach
16:00 – 16:15: Oral Communication 2 – Xiao-Li Pei From Mono- to Bi-metallic Catalysts: Anionic-Arylphosphines-Stabilized Small Gold
and Gold-Silver Clusters
16:15 – 16:30: Oral Communication 3 – Ignacio Pérez-Ortega Benzylic Complexes of Palladium(II): Structure and Reactivity as Precursors of
Palladium Hydrides
16:30 – 16:45: Oral Communication 4 – Daniel Bafaluy Exploring the Copper-Catalyzed N-F Bond Activation toward Intramolecular C-H
Amination
16:45 – 17:00: Oral Communication 5 – Giacomo E. M. Crisenza Asymmetric Photocatalytic C-H Functionalization of Toluene and Derivatives
17:00 – 17:30: Coffee Break (Registered Participants)
Chaiperson: Catherine Holden
17:30 – 18:45: Plenary Lecture 2 – Prof. Timothy Noël Go With the Flow, or Not? The Basic Principles of Flow Chemistry for Synthetic
Organic Chemists
18:45 – 20:00: Oral Communications
18:45 – 19:00: Oral Communication 6 – Irene Giménez-Nueno Iodine-(III) Mediated Diene Aziridination/Ring-Opening. A General Strategy for the
Synthesis of SK1 Inhibitors
19:00 – 19:15: Oral Communication 7 – Joan González-Fabra Multiscale Metadynamics as a Tool for Exploring Reactivity
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19:15 – 19:30: Oral Communication 8 – Jaime Ponce de León Quantifying Coupling Barriers of Ligands Towards NiII/Ni0 Reductive Elimination
19:30 – 19:45: Oral Communication 9 – José Enrique Gómez Copper-Catalyzed Enantioselective Construction of Tertiary Propargylic Sulfones
19:45 – 20:00: Oral Communication 10 – Luis Escobar Reactivity of Encapsulated Guests by Synthetic Receptors in Water
20:30: ICIQ-INTECAT School Dinner (Offered by RedINTECAT. Speakers,
Organizing Committee and registered participants)
Wednesday, 12th December
Chaiperson: Joan Saltó
09:00 – 10:30: Oral Communications
09:00 – 09:15: Oral Communication 11 – Maria Biosca Design of Tailor-Made P,S-Ligand Libraries for C-H and C-X Bond Forming
Reactions in the Framework of INTECAT
09:15 – 09:30: Oral Communication 12 – Marino Börjesson Ni-Catalyzed sp2 C-H Carboxylation via [1,4]-Hydride Shift
09:30 – 09:45: Oral Communication 13 – Zoel Homigón Mechanistic Study on the Synthesis of Glycerol Dialkylethers
09:45 – 10:00: Oral Communication 14 – Mauro Fianchini Stereoselectivity “on Screen”: Understanding Organic Selection by Computational
Means
10:00 – 10:15: Oral Communication 15 – Santiago Cañellas Nickel-Catalyzed Reductive [2+2]-Cyloaddition of Alkynes Towards Cyclobutenes
10:15 – 10:30: Oral Communication 16 – Esther Alza Efficient Reaction Technologies for Novel Chemistry
10:30 – 11:00: Coffee Break (Registered Participants)
Chaiperson: Aijie Cai
11:00 – 12:15: Plenary Lecture 3 - Prof. Dr. Philippe Renaud Organoboron Derivatives in Radical Chemistry
12:15 - 13:30: Plenary Lecture 4 - Prof. Dr. Peter R. Schreiner London Dispersion Effects in Molecular Chemistry – Reconsidering Steric Effects
13:30 – 16:00: Lunch & Poster Session (Offered by RedINTECAT. Speakers,
Organizing Committee and registered participants)
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Chaiperson: Raúl Martín
16:00 – 17:15: Invited Lecture 1 – Prof. José M. González Catalytic Electrophilic Activation of Allenamides: Cycloaddition Reactions and
Further Synthetic Transformations
17:15 – 18:30: Plenary Lecture 5 – Prof. Keary M. Engle Nucleopalladation Reactions: A Historial Perspective
18:30 – 19:00: Coffee Break (Registered Participants)
Chaiperson: Vicente Dorado
19:00 – 20:15: Plenary Lecture 6 – Prof. Timothy Noël Innovation in Catalytic Methodology Development Through Flow Chemistry
20:30: ICIQ-INTECAT School Dinner & Poster Session (Offered by RedINTECAT.
Speakers, Organizing Committee and registered participants)
Thursday, 13th December
Chaiperson: Helena Armengol
09:00 – 10:15: Plenary Lecture 7 – Prof. Keary M. Engle Catalytic Methods for Selective Functionalization of C–C π-Bonds
10:15 – 11:30: Invited Lecture 2 – Prof. J. C. (Chris) Slootweg Circular Chemistry, (formal) N2 Activation and Steric Attraction: New Adventures in
Main-Group Chemistry
11:30 – 12:00: Coffee Break (Registered Participants)
Chaiperson: Marconi N. Peñas de Frutos
12:00 – 13:15: Plenary Lecture 8 – Prof. Dr. Philippe Renaud Extending the Scope of Radical Chain Reactions
13:15 – 15:00: Lunch (Offered by RedINTECAT. Speakers, Organizing Committee
and registered participants)
15:00 – 16:00: Meeting GL + Intecat
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ABSTRACTS
PLENARY LECTURES
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Plenary Lecture 1
Peter R. Schreiner
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Tunneling Control of Chemical Reactions[1]
Peter R. Schreiner
Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 17,
35392 Giessen, Germany
Chemical reactivity is traditionally understood[2] in terms of
kinetic versus thermodynamic control,[3] wherein the driving force is the lowest activation barrier among the possible
reaction paths or the lowest free energy of the final products, respectively. Here we expose quantum mechanical tunneling as
a third driving force that can overwrite traditional kinetic control and govern reactivity based on nonclassical penetration
of the potential energy barriers connecting the reactants and products. These findings are exemplified with the first experimental isolation and full
spectroscopic and theoretical characterization of the elusive hydroxycarbenes (R–C–OH)[4] that undergo facile [1,2]hydrogen tunneling to the corresponding
aldehydes under barriers of nearly 30.0 kcal mol–1 with half-lives of around 1–2 h even at 10 K, despite of the presence of paths with substantially lower
barriers. We will demonstrate that this is a general phenomenon,[5] as exemplified by other OH-tunneling examples such as the rotational
isomerization of a variety of carbocylic acids.[6] Such tunneling processes do not merely represent corrections to the reaction rate, they are the reaction rate,
i.e., the completely control the reaction outome.[1a] They can also override common notions such as the Curtin-Hammett principle.[7]
Finally, we will –for the first time– introduce a tunneling product, i.e., a product of a chemical reaction that can, from a given starting material, only
form through a tunneling process as it is otherwise inaccessible kinetically or thermodynamically.[8]
References
[1] a) P. R. Schreiner, H. P. Reisenauer, D. Ley, D. Gerbig, C.-H. Wu, W. D. Allen, Science 2011, 332, 1300; b) D. Ley, D. Gerbig, P. R. Schreiner, Org.
Biomol. Chem. 2012, 19, 3769; c) D. Gerbig, P. R. Schreiner, Tunnel ing i n the reactions of Carbenes and Oxacarbenes, John Wiley & Sons, Inc.,
Hoboken, 2014; d) P. R. Schreiner, J. Am. Chem. Soc. 2017, 139, 15276. [2] a) H. Eyring, J. Chem. Phys. 1935, 3, 107; b) M. G. Evans, M. Polanyi,
Trans. Faraday Soc. 1935, 31, 875.
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Plenary Lecture 2
Timothy Noël
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Go With the Flow, or Not? The Basic Principles of Flow Chemistry for Synthetic
Organic Chemists
Timothy Noel*
Department of Chemical Engineering and Chemistry, Eindhoven University of Technology University, Groene Loper 5 (STO 1.37), 5612 AE Eindhoven, The
Netherlands.
* [email protected]; Website : www.NoelResearchGroup.com
Flow chemistry is typically used to enable challenging reactions which are difficult to carry out in conventional batch equipment. Consequently, the use of
continuous-flow reactors for applications in organometallic and organic chemistry has witnessed a spectacular increase in interest from the chemistry
community in the last decade. However, flow chemistry is more than just pumping reagents through a capillary and the engineering behind the observed
phenomena can help to exploit the technology’s full potential. Here, we aim to give a concise overview of the most important engineering
aspects associated with flow chemistry, such as mixing, heat transfer, multistep reaction sequences, etc. In addition, we will give suitable chemistry examples
where appropriate to demonstrate the impact of flow processing on synthetic organic chemistry.
References
1. T. Noel, Y. Su, V. Hesssel, Top. Organomet. Chem. 2016, 57, 1-41.
12
Plenary Lecture 3
Philippe Renaud
ICIQ - INTECAT School | Abstract ICIQ - INTECAT School | Abstract
Organoboron Derivatives in Radical Chemistry
Philippe Renaud
Department of Chemsitry and Biochemistry, Freiestrasse 3 University of Bern, 3012 Bern, Switzerland
The ability of organoboron compounds to participate in free radical reactions
has been identified since the earliest investigation of their chemistry. Taming the radical reactivity of organoboranes was a slow process but, eventually, it
led to an extremely valuable alternative to tin chemistry for a wide range of reactions.[1-2] The low toxicity of boric acids derivatives that are usually formed
at the end of the processes makes this chemistry particularly promising for synthesis and industrial applications can be envisaged. The distinctive
properties of boron derivatives make them suitable for the achievement of some unique transformations. This presentation will mainly focus on recent
developments but basic principles and key discoveries will be briefly described to give a general picture of the field. The following point will be presented:
- organoboranes as a source of radicals
- generation of radical via oxidative processes
- organoboranes as chain transfer reagent
- reducing agents involving boron species
- generation and use of boryl radicals
- boron containing radical traps
[1] P. Renaud, in Encyclopedia of Radicals in Chemistry, Biology and Materials, Vol. 2 (Synthetic Strategies and Applications) (Eds.: C.
Chatgilialoglu, A. Studer), John Wiley & Sons, Ltd, Chichester, UK, 2012.
[2] V. Darmency, P. Renaud, Top. Curr. Chem. 2006, 263, 71-106.
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Plenary Lecture 4
Peter R. Schreiner
ICIQ - INTECAT School | Abstract ICIQ - INTECAT School | Abstract
[London Dispersion Effects in Molecular Chemistry –
Reconsidering Steric Effects [1]]
Peter R. Schreiner
Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 17,
35392 Giessen, Germany
[email protected], ORCID: 0000-0002-3608-5515
The Gecko can walk up a glass window because of the adhesion in
hydrophobic setae on its toes that convey van der Waals (vdW) interactions with the surface.[2] The attractive part of such vdW-
interactions is an electron correlation effect referred to as London dispersion. Its role in the formation of condensed matter has been
known since the work of van der Waals[3] and London[4] who related dispersion to polarizability. London dispersion has been
underappreciated in molecular chemistry as a key element of structural stability, chemical reactivity, and catalysis. This negligence is due to the notion
that dispersion is weak, which is only true for one pair of interacting atoms. For increasingly larger structures, the overall dispersion contribution grows rapidly
and can amount to tens of kcal mol–1. This presentation shows selected examples that emphasize the importance of inter- and intramolecular dispersion
for molecules consisting mostly of first row atoms.[5] We note the synergy of experiment and theory that now has reached a stage where dispersion effects
can be examined in fine detail. This forces us to re-consider our perception of steric hindrance and stereoelectronic effects, and even the transferability of
chemical bond parameters from one molecule to another.
References
[1] J. P. Wagner, P. R. Schreiner, Angew. Chem. Int. Ed. 2015, 54, 12274. [2] K. Autumn, M. Sitti, Y. A. Liang, A. M. Peattie, W. R. Hansen, S.
Sponberg, T. W. Kenny, R. Fearing, J. N. Israelachvili, R. J. Full, Proc. Natl. Acad. Sci. 2002, 99, 12252.
[3] J. D. van der Waals, Over de Continuiteit van den Gasen Vloeistoftoestand Leiden University (Leiden, The Netherlands), 1873.
[4] F. London, Z. Phys. 1930, 63, 245. [5] a) S. Rösel, C. Balestrieri, P. R. Schreiner, Chem. Sci. 2017, 8, 405; b) J. P .
Wagner, P. R. Schreiner, J. Chem. Theory Comput. 2016, 12, 231; c) E. Prochazkova, A. Kolmer, J. Ilgen, M. Schwab, L. Kaltschnee, M.
Fredersdorf, V. Schmidts, R. C. Wende, P. R. Schreiner, C. M. Thiele,
14
Plenary Lecture 5
Keary M. Engle
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Nucleopalladation Reactions: A Historial Perspective
Keary M. Englea*
a, The Scripps Research Institute, 10550 N. Torrey Pines Rd., La Jolla, CA 92037
The discovery and development of the Wacker oxidation, the Fujiwara–
Motitani reaction, and the Mizoroki–Heck coupling in the 1960s and 1970s established the foundation for organopalladium chemistry and ushered in the
modern era of homogenous catalysis (Scheme 1).1–3 These venerable alkene functionalization reactions continue to be a rich source of inspiration for
ongoing research efforts across the world, including those within our laboratory at Scripps Research. This lecture will describe key discoveries in this area of
research and will highlight key mechanistic principles that have emerged during the last half-century of studying these reaction systems. The goal of this
tutorial will be to equip attendees with a rigorous understanding of nucleopalladation reactivity, such that they can appreciate contemporary
research on this topic and identify important new opportunities for exploration.
References
1. R. Jira, Angew. Chem. Int. Ed. 2009, 48, 9034–9037. 2. J. A. Keith, P. M. Henry, Angew. Chem. Int. Ed. 2009, 48, 9038–9049.
3. R. F. Heck, Acc. Chem. Res. 2002, 12, 146–151.
R
alkenes
R
Nu
or
RNu
cat. PdII
[O], [Nu]
cat. Pd0
[E]
R
E
or
RE
Mizoroki–Heck WackerFujiwara–Moritani
[Ar–I, Alkyl–I, N–O, etc.]
[Ar–H, H2O, R'2NH, etc.]
Scheme 1: General overview of nucleopalladation reactions.
15
Plenary Lecture 6
Timothy Noël
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Innovation in catalytic methodology development through flow chemistry
Timothy Noel*
Department of Chemical Engineering and Chemistry, Eindhoven University of
Technology University, Groene Loper 5 (STO 1.37), 5612 AE Eindhoven, The Netherlands.
* [email protected]; Website : www.NoelResearchGroup.com
Until recently, many reactions have been exclusively performed in
conventional batch LabWare. With the advent of microreactor technology, significant effort has been devoted to develop a wide variety of continuous-
flow techniques to facilitate organic synthesis. Microreactor technology offers several advantages compared to traditional batch reactors, such as, enhanced
heat- and mass-transfer, improved irradiation, safety of operation and the possibility to integrate several reaction steps and subsequent separations in a
single streamlined process.1 My group has taken a great interest in assisting chemists by developing
automated and flow-based reaction technologies capable of reducing manual labor, increasing the reproducibility of the results and accelerating reaction
discovery. In this presentation, we will give an overview of our catalytic methodology development, exemplified by photoredox catalysis2 and C–H
activation chemistry,3 and how these synthetic methods were impacted by continuous-flow microreactor technology. Furthermore, we will discuss the
developed technology and reaction models in detail.
References 1. (a) H. P. L. Gemoets, Y. Su, M. Shang, V. Hessel, R. Luque, T. Noel, Chem .
Soc. Rev. 2016, 45, 83-117. (b) D. Cambie, C. Bottecchia, N. J. W. Straathof, V. Hessel, T. Noel, Chem. Rev. 2016, 116, 10276-10341.
2. (a) X.-J. Wei, W. Boon, V. Hessel, T. Noel, ACS Catal. 2017, 7, 7136-7140. (b) C. Bottecchia, M. Rubens, S. Gunnoo, V. Hessel, A. Madder, T. Noel,
Angew. Chem. Int. Ed. 2017, 56, 12701-12707. (c) D. Cambie, F. Zhao, V. Hessel, M. G. Debije, T. Noel, Angew. Chem. Int. Ed. 2017, 56, 1050-1054. (d)
N. J. W. Straathof, S. E. Cramer, V. Hessel, T. Noel, Angew. Chem. Int. Ed. 2016, 55, 15549-15553.
3. (a) G. Laudadio, S. Govaerts, Y. Wang, D. Ravelli, H. F. Koolman, M. Fagnoni, S. W. Djuric, T. Noel, Angew. Chem. Int. Ed. 2018, 57, 4078-4082. .
(b) H. P. L. Gemoets, G. Laudadio, K. Verstraete, V. Hessel, T. Noel, Angew. Chem. Int. Ed. 2017, 56, 7161-7165. (c) U. K. Sharma, H. P. L. Gemoets, F.
Schoeder, T. Noel, E Van der Eycken, ACS Catal. 2017, 7, 3818-3823.
16
Plenary Lecture 7
Keary M. Engle
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Catalytic Methods for Selective Functionalization of C–C π-Bonds
Keary M. Englea*
a, The Scripps Research Institute, 10550 N. Torrey Pines Rd., La Jolla, CA
92037 * [email protected]
Vicinal (1,2-disubstituted) functional group motifs are ubiquitous in structurally complex small molecules that are of
academic and industrial importance, including many widely used pharmaceutical agents. Many such functional group combinations,
however, remain exceptionally challenging to synthesize. The goal of research in the Engle lab is to develop a general catalytic platform
for alkene and alkyne difunctionalization to introduce a diverse array of functional groups at each of the two carbon atoms in a programmable
fashion. Our central hypothesis is that is that coordination of a π-Lewis acidic metal, such as palladium(II), to the alkene will
promote nucleophilic attack and that the resultant organometallic species can be trapped with an electrophile to furnish the desired
1,2-difunctionalized product. In the overall net transformation, one of the two new functional groups is introduced in the form of a
nucleophile, and the other in the form of an electrophile. Directing groups are used to control the regiochemical course of the reaction
and stabilize key alkylmetal intermediates. These concepts have been used to expand the synthetic toolkit to include new retrosynthetic
disconnections, including “homo-Michael” addition and β,γ-vicinal dicarbofunctionalization of alkenyl carbonyl compounds.1
References
1. J. A. Gurak Jr., K. M. Engle, Synlett 2017, 28, 2057–2065.
R'
R '
Nu
[Mn]
R
R
[Mn]
R'
Nu
[Mn+2]
R
E
R'
Nu
E
R
X
+
Nu–
E+
M = CuI, PdII, PtII, etc.
nucleo-metalation
reductiveelimination
oxidativeaddition
R1
R2R3
R4
R1
R2
R3
R4
E Nu
E, Nu = H, C, O, N, F, etc.
• programmable• combinatorial• stereoselective
M (cat.), Nu–, E+
Ixabepilone® Taxol®
A. inspiration: commercial anti-cancer drugs
HN
O OH O
Me
OHMe
Me Me
OMe
MeS
NMe
Me
Me
Me
AcO O OH
OAc
O
HO OBz
Me
O
O
Ph
OH
NHBz
B. approach: expedient access from simple alkenes
C. design: modular catalytic cycle
(alkenes)renewable feedstocks
17
Plenary Lecture 8
Philippe Renaud
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Extending the Scope of Radical Chain Reactions
Philippe Renaud
Department of Chemsitry and Biochemistry, Freiestrasse 3 University of Bern, 3012 Bern, Switzerland
The first part of the lecture will focus on the utility of radical chain reactions
for the formation of C–H(D),[1] C–C,[2] C–N[3] and C–F[4] bonds under mild conditions. The importance of enthalpic and polar effects will be highlighted.
The second part will be dedicated to a new approach to increase the efficiency of chain reactions. The concept of repair is widely used by nature to heal
molecules such as proteins, lipids, sugars and DNA that are damaged by hydrogen atom abstraction resulting from oxidative stress. This strategy, rather
undocumented in the field of synthetic organic chemistry, can be used in a radical chain reaction to enable notoriously intractable transformations. By
overcoming the radical chain inhibitor properties of substituted alkenes, the radical-mediated hydroalkylation of mono-, di-, tri-, and even tetrasubstituted
unactivated olefins could be performed under mild conditions.[5] With a remarkable functional group tolerance, this reaction provides a general
coupling method for the derivatization of olefin containing natural products.
[1] V. Soulard, G. Villa, D. P. Vollmar, P. Renaud, J. Am. Chem. Soc. 2018 , 140, 155-158.
[2] C. S. Gloor, F. Dénès, P. Renaud, Angew. Chem. Int. Ed. 2017, 36.
[3] D. Meyer, P. Renaud, Angew. Chem. Int. Ed. 2017, 56, 10858-10861.
[4] D. Meyer, H. Jangra, F. Walther, H. Zipse, P. Renaud, Nature Commun. 2018, in press.
[5] G. Povie, S. R. Suravarapu, M. P. Bircher, M. M. Mojzes, S. Rieder, P. Renaud, Science Adv. 2018, 4, eaat6031.
18
ABSTRACTS
INVITED LECTURES
19
Invited Lecture 1
José M. González
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Catalytic Electrophilic Activation of Allenamides: Cycloaddition Reactions and Further Synthetic
Transformations
José M. González Instituto Universitario de Química Organometálica “Enrique Moles” and
Departamento de Química Orgánica e Inorgánica, Universidad de Oviedo, C/ Julián Clavería, 8, Oviedo 33006
The reaction of different classes of unsaturated systems with a variety of
electrophiles results in powerful methodologies for their facile and rapid functionalization. Not only transformations relying on the reactivity of
stoichiometric reagents but also catalytic alternatives have been developed. Our laboratory has been active in both scenarios.1
In this presentation some features related to the reactivity of allenamides under
the influence of gold(I) catalysis will be outlined.2 Attention will be also devoted to some additional transformation of the products arising from those
catalytic reactions, which lead to the assembly of attractive structural motifs, in a straightforward manner.3
References
1. S. Suárez-Pantiga, J. M. González, Pure Appl. Chem.. 2013, 85, 721-739. 2. Some examples: a) S. Suárez-Pantiga, C. Hernández-Díaz, E. Rubio, J. M.
González, Angew. Chem. Int. Ed. 2012, 51, 11552-1155; b).C. Hernández-Díaz, E. Rubio, J. M. González, Eur. J. Org. Chem. 2016, 265-269; c) A. Ballesteros ,
P. Morán-Poladura, J. M. González, Chem.Commun. 2016, 52, 2905-2908. 3. A. Ballesteros, J. M. González, unpublished results.
20
Invited Lecture 2
J. Chris Slootweg
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Circular Chemistry, (formal) N2 Activation and Steric Attraction: New Adventures in Main-Group Chemistry
J. Chris Slootwega*
a, Van 't Hoff Institute for Molecular Sciences, University of Amsterdam
Science Park 904, 1098 XH Amsterdam, The Netherlands * [email protected]
While the well-known Green Chemistry principles focus on optimizing and
sustaining linear processes, circular chemistry moves beyond value extension and aims at making chemical processes and production cycles truly circular.
In this lecture, I will introduce Circular Chemistry as a new concept,1 discuss
the 12 principles of circular chemistry and highlight these important concepts with appealing examples focussing on the sustainable use of phosphorus and
nitrogen.
After this holistic view on chemistry, I will focus on our bottom-up approach using the complete physical organic chemistry toolbox and highlight our new
adventures in main-group chemistry for the activation and functionalization of small molecules.
References
1. T. Keijer, V. Bakker, J.C. Slootweg, Nature Chem. 2018, accepted
21
ABSTRACTS
ORAL COMMUNICATIONS
22
Oral Communication 1
Antoni Llobet
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
New Energy Conversion Schemes: A Molecular Approach
Antoni Llobet Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of
Science and Technology (BIST), Av. Països Catalans 16, E-43007 Tarragona,
Spain and Departament de Química Universitat Autònoma de Barcelona, Cerdanyola del Vallès, E-08193 Barcelona, Spain.
The replacement of fossil fuels by a clean and renewable energy source is one
of the most urgent and challenging issues our society is facing today, which is why intense research efforts are devoted to this topic recently. Nature has been
using sunlight as the primary energy input to oxidize water and generate carbohydrates (a solar fuel) for over a billion years. Inspired, but not
constrained by nature, artificial systems1 can be designed to capture light and oxidize water and reduce protons or other organic compounds to generate
useful chemical fuels.
Figure 1. A cartoon showing the performance of a hybrid molecular photoanode for light induced
water oxidation.
In this context this contribution will present how molecular catalysts can be anchored on solid supports to generate powerful hybrid electro- and photo-
anodes and cathodes for water splitting and other applications.2
References
1. P. Garrido-Barros, A. Llobet, Chem. Soc. Rev., 2017, 46, 6088-6098.
2. (a) L. Duan, A. Llobet et al., Nat. Chem 2012, 4, 418-423, (b) D. Moonshiram, A. Llobet, J. Am. Chem. Soc. 2016, 138, 10586-10596, (c) C.
Gimbert, A. Llobet, A. et al. J. Am. Chem. Soc. 2016, 138, 15291-15294, (d) Matheu, A. Llobet, et al., J. Am. Chem. Soc. 2017, 139, 11345-11348, (e) P.
Garrido-Barros, A. Llobet et al., J. Am. Chem. Soc. 2017, 139, 12907-12910.
23
Oral Communication 2
Xiao-Li Pei
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
From Mono- to Bi-metallic Catalysts: Anionic-Arylphosphines-Stabilized Small Gold and Gold-Silver
Clusters
Xiao-Li Peia*, Ekaterina S. Smirnovaa, Ana Pereiraa, Antonio M. Echavarrenab
a, Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of Science and Technology, Av. Paisos Catalans 16, Tarragona,
b, Departament de Química Analítica i Química Orgànica, Universitat Rovira i
Virgili, Av. Paisos Catalans 16, Tarragona. * [email protected]
Gold or heterometallic gold-silver systems, especially metal clusters and nanoparticles, have attracted widely research interests in these decades, due to
their potential application in catalysis, sensors, bio-image and etc.1 Particularly inspired by the highly efficient catalytic activities of very small sized gold
clusters in organic transformations,2,3 we anticipated that small gold(I)/gold(I)-silver(I) clusters might be rationally designed by AuI/Si transmetallation with
potentially hemilabile phosphines (ortho-silylphosphine ligands), based on the previous studies in hexagold clusters. Herein, we report the successful isolation
of a family of small gold and gold-silver clusters, and show their interesting structure-related activities in the activation of internal and terminal alkynes
with the representative Au-catalyzed transformations.
References
1. Gimeno, M. C.; Laguna, A. Chem. Soc. Rev. 2008, 37, 1952-1966. 2. R. Jin, C. Zeng, M. Zhou, Y. Chen, Chem. Rev. 2016, 116, 10346-10413.
3. J. Oliver-Meseguer, J. R. Cabrero-Antonino, I. Domínguez, A. Leyva-Pérez, A. Corma,
Science 2012, 338, 1452-1455.
24
Oral Communication 3
Ignacio Pérez-Ortega
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Benzylic Complexes of Palladium(II): Structure and
Reactivity as Precursors of Palladium Hydrides.
Ignacio Pérez-Ortega, Blanca Martín-Ruiz, Ana C. Albéniz* IU CINQUIMA/Química Inorgánica. Universidad de Valladolid. E-47071
Valladolid. Spain [email protected]
We have synthesized a large variety of palladium benzylic complexes bearing a
-CH2C6F5 substituent by addition of different type and number of ligands to
complex 1 (Figure 1). With the bulky ligands PPh3, AsPh3 or dppf the adopti on
of a pentacoordinated h3-benzylic complex is favorable (Figure 1).
Figure 1.
All complexes decompose by b-Hydrogen elimination to give 2 and a
palladium hydride. This hydride either decomposes or it is transferred to
another complex molecule to give the reduction product 3 (Figure 1). On the
other hand, the Pd-H fragment can be trapped by insertion of an
enantiomerically pure diene into the Pd-H moiety to generate a
enantiomerically pure allyl complex.
Acknowledgements: We are grateful to the Spanish MINECO (SGPI, grant
CTQ2016-80913-P) for financial support.
25
Oral Communication 4
Daniel Bafaluy
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Exploring the Copper-Catalyzed N-F Bond Activation toward Intramolecular C-H Amination
Daniel Bafaluya*, Kilian Muñizb
a, Institute of Chemical Research of Catalonia(ICIQ), 16 Avgda. Països
Catalans, 43007 Tarragona, Spain. b, ICREA, Pg. Lluís Companys 23, 08010 Barcelona, Spain.
N-halogenated amines are widely studied functionalities as radical precursors in oxidative chemistry.1 Particularly, such type of compounds have been used in
intramolecular C-H halogenation and/or amination reactions.2 In this context, N-X bonds where X=I, Br, Cl have been exploited, however, the analogous
fluorinated series is neglected in the literature for C-H functionalization with few exceptions.3
We recently developed a copper catalyzed activation of N-F bonds for
intramolecular C-H amination, where the fluorinated amine acts both as oxidant and nitrogen source for the amination event. With this new protocol we can
access both pyrrolidine and piperidine formation in a selective manner. In addition, computational studies were performed to gain insight at the
unconventional mechanism of the transformation.4
References
1. S. Minakata, Acc. Chem. Res. 2009, 42, 1172. 2. Selected examples: a) C. Martínez, K. Muñiz, Angew. Chem. Int. Ed. 2015,
54, 8287. b) P. Becker, T. Duhamel, C. Martínez, K. Muñiz, Angew. Chem. Int . Ed. 2018, 57, 5166.
3. B. J. Groendyke, D. I. AbuSalim, S. P. Cook, J. Am. Chem. Soc. 2016 , 138 , 12771.
4. D. Bafaluy, J. M. Muñoz-Molina, I. Funes-Ardoiz, S. Herold, H. Zhang, F. Maseras, T. R. Belderrain, P. J. Pérez, K. Muñiz, submitted.
Ar XN
R'
F
1% TpiPr2Cu(NCMe)
Toluene, 100 Â˚C24 h
X
N
R'
Ar
n = 1, 2X = CH2, O
H Rn
selective to
pyrrolidines or
piperidines
~ 28 examples
up to 99% yield
n
n
Rn
H
(-HF)
H
26
Oral Communication 5
Giacomo E. M. Crisenza
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Asymmetric Photocatalytic C-H Functionalization of Toluene and Derivatives
Dr Giacomo E. M. Crisenzaa*, Daniele Mazzarellaa, Prof. Paolo Melchiorrea,b
a, ICIQ, Av. Països Catalans 16 – 43007 Tarragona (Spain).
b, IIT, via Morego 30 – 16163 Genoa (Italy) * [email protected]
The emerging field of photoredox catalysis has led to the development of new transformations due to the ability to generate radical intermediates under mild conditions.1 Traditionally, this relies on a photocatalyst which efficiently absorbs l igh t
and induces a single electron transfer (SET). Recently, our group proved that a SET event can be triggered by the direct visible-light excitation of organocatalytic intermediates, unlocking reaction manifolds that are unavailable to conventional ground-
state organocatalytic pathways.2a In particular, we demonstrated that photolytically generated excited-state chiral iminium ions act as strong SET oxidants, enabling the enantioselective β-functionalization of enals in combination with reaction partners
bearing suitable electron-auxiliary functionalities.2b-d To further expand the synthetic potential of this reactivity, we wondered whe th er t hi s
could be applied to the direct asymmetric C-H functionalization of simple toluene derivatives. This strategy is attractive as it utilizes highly available feedstock chemicals and visible-light for making chiral molecules. While the use of toluene has already been
reported in photoredox processes,3 its employment in asymmetric catalysis has remained elusive. This reactivity has been achieved by coupling the enhanced oxidizing capability of
excited-state iminium ion with the basic character of its counter-anion to trigger a proton-coupled electron transfer pathway. This generates reactive benzylic radicals directly from the corresponding unfunctionalized precursors. The transformation
proceeds under mild conditions and delivers the desired β-alkylated products genera ll y in high yield and with good enantioselectivity.4
References
1. M. H. Shaw, J. Twilton, D. W. C. MacMillan J. Org. Chem. 2016, 81, 6898. 2. a) M. Silvi, P. Melchiorre, Nature 2018 , 554, 41, and selected contributions by
Melchiorre and co-workers: b) Nat. Chem. 2017 , 9, 868; c) Angew. Chem. Int.
Ed. 2018, 57, 1068; d) ACS Catal. 2018, 8, 1062. 3. Selected examples: a) K. Ohkubo, K. Mizushima, R. Iwata, K. Souma, N. Suzuki, S.
Fukuzumi Chem. Commun. 2010, 46, 601; b) R. Zhuo, H. Liu, H. Tao, X. Yu, J. Wu
Chem. Sci. 2017, 8, 4654. 4. D. Mazzarella, G. E. M. Crisenza, P. Melchiorre J. Am. Chem. Soc. 2018, 140, 8443.
27
Oral Communication 6
I. Giménez-Nueno
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Iodine-(III) mediated diene aziridination/ring-opening. A general strategy for the synthesis of SK1 inhibitors.
I. Giménez-Nuenoa*, J. Guascha, M. I. Matheua, S. Castillóna, Y. Díaza
a Departament de Química Analítica I Química Orgànica, Fac. Química
Universitat Rovira i Virgilli, C/ Marcel·lí Domingo 1, 43007, Tarragona, Spain* *[email protected]
Sphingolipids play a central role in cancer processes. Recently, the inhibition of
Sphingosine Kinase 1 (SK1) by sphingosine analogues has been reported to
promote cell apoptosis, thus creating new opportunities for cancer treatment.1
Along these lines, a nitrene transfer reaction to dienes was envisioned to furnish
the desired vinylaziridine precursor for the synthesis of former sphingosine
analogues (Scheme 1).
Previous work within the group involved the intramolecular aziridination of
dienyl carbamates using a rhodium catalyst.2 Interestingly, when this substrate
was reacted in the presence of PhIO, no metal-catalyst was required for the
aziridination process. The development and optimization of a iodine(III)-
mediated diene aziridination/ring-opening and its application to the
enantioselective synthesis of sphingosine analogues will be presented.3
References 1 D. Plano, S. Amin, A. K. Sharma, J. Med. Chem. 2014, 57, 5509-5524. 2 J. Guasch, Y. Díaz, M. I. Matheu, S. Castillón, Chem. Commun. 2014, 50, 7344-7347. 3 J. Guasch, I. Giménez-Nueno, I. Funes-Ardoiz, M. Bernús, M. I. Matheu, F. Maseras ,
S. Castillón, Y. Díaz, Chem. Eur. J. 2018, 24, 4635-4642.
28
Oral Communication 7
Joan González-Fabra
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Multiscale Metadynamics as a Tool for Exploring Reactivity
Joan González-Fabraa*, Carles Boa,b
a, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of
Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain. b, Departament de Química Física i Inorgànica, Universitat Rovira i Virgili,
Marcel·lí Domingo s/n, 43007 Tarragona, Spain.
Carbon dioxide (CO2) is one of the main pollutants produced nowadays, its constant expelling to the atmosphere leads to the well-known phenomena of
global warming. This problem can be mitigated through the chemical fixation of CO2 into molecules using CO2 as C1 building block.
In our group we have elucidated the mechanisms of reactions to produce polycarbonates1 or cyclic carbonates2 from CO2 and epoxides by means of
DFT-based methods. Lately we concerned in the decarboxylation reaction and the effect of CO2 pressure in its rate.
Standard static DFT-based methods are not appropriate to describe in detail the effect of CO2 pressure. Alternatively, molecular dynamics allow to simulate a
more realistic model of the entire system including the relative concentrations of all species and the total pressure applied to the system. Consequently, a
multiscale metadynamics method3 has been used to simulate the reaction mechanism and to study the variation of the Gibbs free-energy barrier by
changing the CO2 pressure.
References 1. (a) L. Peña Carrodeguas, J. González-Fabra, F. Castro-Gómez, C. Bo, A. W. Kleij Chem. Eur. J. 2015, 21, 6115. (b) J. González-Fabra, F. Castro-Gómez, A. W. Kleij, C .
Bo ChemSusChem, 2017, 10, 1233 - 1240. 2. C. J. Whiteoak, N. Kielland, V. Laserna, F. Castro-Gómez, E. Martin, E. C. Escudero-Adán, C. Bo, A. W. Kleij, Chemsitry – A European Journal 2014, 20, 2264-2270.
3. J. M. Boereboom, R. Potestio, D. Donadio, R. E. Bulo J. Chem. Theory Comput. 2016 , 12, 3441-3448.
29
Oral Communication 8
Jaime Ponce de León
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Quantifying coupling barriers of ligands towards NiII/Ni0 reductive elimination.
Jaime Ponce de León, Estefania Gioria, Pablo Espinet*
I.U. CINQUIMA / Química Inorgánica, Facultad de Ciencias, Universidad de Valladolid, 47011, Valladolid, Spain
Abstract text: A NiII complex, cis-[Ni(C6F5)2(THF)2] (1), is presented as a
synthon of cis-Ni(C6F5)2 that can be used as a meter of the ligand effect on NiIIàNi0 reductive elimination (coupling) processes upon ligand addition
(Scheme 1). The complex is easily obtained from commercially available NiBr2(dme) (or NiCl2(dme)) in an improved one-step synthesis. Several ligands
of different types were tested: a) heterocyclic N-type ligands (bipyridines); b) chelating diphosphines; c) monodentate phosphines; d) Buchwald type
phosphines (dialkylbiaryl phosphines); e) PEWO (phosphine-electron-withdrawing olefin chelate) ligands.
Extremely different C6F5–C6F5 coupling rates were observed at 25 °C for the different ligands, ranging from totally inactive to almost instantaneous. PEWO
type ligands are extraordinarily efficient, producing that challenging coupling almost instantaneously even at –55 °C, with total conversion and coupling vs.
hydrolysis selectivity. They provide the lowest, by several orders of magnitude, coupling barriers ever observed from Ar2NiII complexes.
30
Oral Communication 9
José Enrique Gómez
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Copper-Catalyzed Enantioselective Construction of Tertiary
Propargylic Sulfones
José Enrique Gómez,† Àlex Cristòfol,† and Arjan W. Kleij*,†,§
†Institute of Chemical Research of Catalonia (ICIQ), the Barcelona Institute of
Science and Technology, Av. Països Catalans 16, 43007 – Tarragona, Spain
§Catalan Institute of Research and Advanced Studies (ICREA), Pg. Lluís
Companys 23, 08010 – Barcelona, Spain
Sulfur-containing tetrasubstituted carbon stereocenters are frequently
embedded in numerous natural products, biologically active small molecules
and pharmaceutical ingredients.[1] A general enantioselective synthesis of
propargylic sulfones containing tetrasubtituted tertiary centers is presented.
This approach relies on an unprecedented copper-catalyzed asymmetric
propargylic substitution (APS) reaction of alkynyl cyclic carbonates with
sodium sulfinates.[2] This methodology features good yields and selectivities,
synthetic diversity and wide product scope, and represents the formation of an
important b-hydroxysulfone fragment.
References
[1] Yu, J.-S.; Huang, H.-M.; Ding, P.-G.; Hu, X.-S.; Zhou, F.; Zhou, J . AC S.
Catal. 2016, 6, 5319.
[2] Guo, W.; Gómez, J. E.; Cristofol, A.; Xie, J.; Kleij, A. W. Angew . C hem.
Int. Ed. 2018, 57, 13735.
q Chiral Tertiary Sulfones
q High yields & er values
q Versatile building blocks
q Practical methodology
31
Oral Communication 10
Luis Escobar
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Reactivity of Encapsulated Guests by Synthetic Receptors in Water
Luis Escobara and Pablo Ballestera,b*
a, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of
Science and Technology (BIST), Av. Països Catalans, 16, 43007, Tarragona. b, ICREA, Passeig Lluís Companys, 23, 08010, Barcelona.
Synthetic receptors can impart unusual reactivity to encapsulated guest
molecules. The receptor functions as reaction vessel (e.g. increasing the effective molarity of bound reactants), but can control the selectivity and work
as catalyst as well.1,2 These features make supramolecular catalysts capable of mimicking natural enzymes.
Acetal hydrolysis is usually performed in acidic aqueous media. However, Raymond and co-workers showed that an anionic metal coordination cage is
able to catalyse the above mentioned reaction, but in basic solution (Figure 1a).3
We report here the reactivity of a bound (4-acetal)-substituted pyridyl N-oxide by octa-acid and octa-pyridinium super aryl-extended calix[4]pyrroles4 in
aqueous solution (Figure 1b). The results showed that the super aryl-extended receptors inhibit the hydrolysis of the bound molecule.
Figure 1. Hydrolysis of acetal derivatives in aqueous solution using a) a tetrahedral [Ga4L6]12- cage and b) super aryl-extended calix[4]pyrroles.
References 1. C. J. Brown, F. D. Toste, R. G. Bergman, K. N. Raymond, Chem. Rev.
(Washington, DC, U. S.) 2015, 115, 3012-3035. 2. V. Ramamurthy, Acc. Chem. Res. 2015, 48, 2904-2917.
3. M. D. Pluth, R. G. Bergman, K. N. Raymond, Acc. Chem. Res. 2009, 42, 1650-1659.
4. L. Escobar, G. Aragay, P. Ballester, Chem.--Eur. J. 2016, 22, 13682-13689.
32
Oral Communication 11
Maria Biosca
ICIQ - INTECAT School | Abstract
Design of tailor-made P,S-ligand libraries for C-H and C-X bond forming reactions in the framework of INTECAT
Maria Bioscaa*, Joan Saltóa, Jessica Margalefa, Xisco Caldenteyb, Carles Rodríguez-Escrichb, Maria Besorab, Feliu Maserasb, Miquel A. Pericàsb,
Oscar Pàmiesa and Montserrat Diégueza a, Departament de Química Física i Inorgànica, Universitat Rovira i Virgili,
C/Marcel·lí Domingo, 1, 43007 Tarragona, Spain.
b, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av Països Catalans 16, 43007 Tarragona, Spain.
The growing demand for enantiopure products has stimulated the interest of industry in the search of better synthetic procedures for their production. In this
context, asymmetric catalysis plays a key role because with a small amount of catalyst, large quantities of chiral compounds can be produced with fewer
reaction steps and byproducts. The efficiency of this strategy mainly relies in the correct chose of the catalyst structure. Although, thousands of chiral ligands
have been developed only few of them have shown a general scope. Therefore, the discovery of efficient ligands prepared in a few steps, from cheap starting
materials, easy to handle and that tolerate a broad
range of substrates is still needed. Our group has
expertise in preparing modular and easy to
handle ligand libraries from readily available materials. These ligands provided an improved generation of catalysts for C-H and C-X bond forming reactions
(Scheme 1).1 In this communication, we will present our recent progress in collaboration with INTECAT framework groups in the application of efficient
phosphorus-thioether ligands in these challenging catalytic reactions.2 The simplicity of these ligand libraries allows us to use DFT calculations to guide
the optimal ligand parameters.
References
1. For recent publications: a) R. Bellini, M. Magre, M. Biosca, P.-O. Norrby, O. Pàmies, M. Diéguez, C. Moberg, ACS Catal. 2016, 6, 1701-1712. b) M. Biosca, M. Magre, O. Pàmies, M. Diéguez, ACS Catal. 2018, 8, 10316-10320. 2. a) J. Margalef, X. Caldentey, E. A. Karlsson, M. Coll, J. Mazuela, O. Pàmies, M. Dièguez, M. A. Pericàs, Chem. Eur. J. 2014, 20, 12201-12214. b) M. Biosca, J. Margalef, X. Caldentey, M. Besora, C. Rodríguez-Escrich, J. Saltó, X. C. Cambeiro, F. Maseras, O. Pàmies, M. Diéguez, M. A. Pericàs, ACS Catal. 2018, 8 , 3587–3601.
Scheme 1. C-H and C-X bond forming reactions.
33
Oral Communication 12
Marino Börjesson
ICIQ - INTECAT School | Abstract
34
Oral Communication 13
Zoel Hormigón
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Mechanistic study on the synthesis of glycerol dialkylethers
Zoel Hormigóna, José Ignacio Garcíaa, Alejandro Leal-Duasoa, José
Antonio Mayorala, Elisabet Piresa, Luis Salvatellaa
a, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH). CSIC-Universidad de Zaragoza, Pedro Cerbuna 12, E-50009 Zaragoza.
In the recent years, vegetable oils are regarded as a renewable source of
building blocks, providing fatty esters or acids and glycerol1,2. The valorisat i on of the latter constitutes a critical point, and this is why the use of glycerol and
its derivatives as potential renewable solvents has attracted great attention3. Among them, glycerol ethers present very interesting properties as alternative
solvents due to their chemical stability, low acute ecotoxicity and modifiable physico-chemical properties by changing the number, size, substitution and
nature of the substituents4. The synthesis of symmetric glycerol diethers starting from epichlorohydrin and
several alcohols (methanol, ethanol, 1-butanol, 2-propanol, trifluoroethanol and phenol) in basic media has been studied experimental and theoretically, to
analyse the effect of the alcohol nature both in reactivity and regioselectivity of the reaction.
Through the location of energy minima and transition states more representative of the process, by means of DFT calculations at
CPCM(solvent)/M06-2X/6-311++G(d,p) level, it is possible to rationalise the product distribution and the detection of intermediates such as [R.0.Cl].
References
1. U. Biermann, U. Bornscheuer, M. A. R. Meier, J. O. Metzger, H. J. Schäfer, Angew. Chem. I n t . Ed. 2011, 50, 3854.
2. J. O. Metzger, Eur. J. Lipid Sci. Technol. 2009, 111, 865. 3. J. I. García, H. García-Marín, E. Pires, Green Chem. 2014, 16, 1007. 4. J. I. García, H. García-Marín, J. A. Mayoral, P. Pérez, Green Chem. 2013, 15, 2283.
35
Oral Communication 14
Mauro Fianchini
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Stereoselectivity “on Screen”: Understanding Organic
Selection by Computational Means
Mauro Fianchinia*, Feliu Maserasa,b a, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of
Science and Technology, Avgda Països Catalans, 16, 43007, Tarragona, Spain b, Department de Química, Universitat Autònoma de Barcelona (UAB),Spain
* Presenting or corresponding author: [email protected]
Computational modeling proved to be a prominent way of explaining
experimental results during the last three decades and a robust inexpensive asset to predict chemical properties and behavior1,2. Theoretical models able to
reproduce experimental findings with a high degree of confidence represent a strong support in targeted synthesis. This paper presents to the audience state-
of-the-art approaches in modern computation aimed to address the challenges of stereoselectivity of stoichiometric and catalytic organic species (particularly
those challenges unsolved by trial-and-error synthetic approach). Condensation
reactions, such as [2+2] ketene-imine Staudinger reaction3 (production of b-
lactams) and [2+2] phosphorus ylide-aldehyde Wittig olefination4 (production of olefins), have been chosen as suitable candidates for our investigation.
The study moves from the exploration of hypersurfaces
(stationary points) to involve time- versus-concentrations kinetic
modeling5 (thermodynamics and kinetics of evolving systems) and
finally focuses on a priori generation of chemical descriptors
for reactivity through principal component analysis and/or singular value decomposition. Successes and
challenges embedded in this combined approach will be discussed.
References 1. K.N. Houk, P.H. Cheong, Nature 2008, 455, 309-313. 2. M. Fianchini, Phys. Sci. Rev. 2017, 2, 20170134. 3. L. Jiao, Y. Liang, J. Xu, J. Am. Chem. Soc. 2006, 128, 6060-6069. 4. G. Wittig, U. Schollkopf, Chem. Ber. 1954, 87, 1318–1330. 5. Besora, M.; Maseras, F. WIRES Comput. Mol. Sci. 2018, 8, e1372.
36
Oral Communication 15
Santiago Cañellas
ICIQ - INTECAT School | Abstract
37
Oral Communication 16
Esther Alza
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
EFFICIENT REACTION TECHNOLOGIES FOR NOVEL CHEMISTRY
Esther Alzaa*, Miquel A. Pericàsa
a, Institut Català d’Investigació Química, Avda. Països Catalans, 16, 43007,
Tarragona. * [email protected]
Continuous flow chemistry presents many advantages compared to the
traditional ‘batch’ processes.1 Flow techniques are slowly becoming mainstream practice. This involves that every day more and more labs, in
academia or industry, possess a small collection of pumps and other related gadgets that a few years ago most chemists would have never dreamt of using.2
Despite this, expert pioneers able to guide the different sectors in the paradigm change from batch to flow approaches are needed. This shift is desired in
Research and Development in order to address the challenges of tomorrow.
ERTFLOW is a technology development unit from ICIQ, which aims the development of efficient processes in catalysis and continuous flow for
sustainable chemistry.3 Our team has strong background in organic synthesis and flow chemistry, along with extensive experience in the development of
immobilized (chiral) catalysts and flow systems design. ERTFLOW introduction, key challenges in flow chemistry and applications in laboratory
synthesis and future industrial production will be discussed.
References 1. a) Darvas, F., Dorman G., V. H. Flow Chemistry Organic: Volume 1:
Fundamentals. (Walter de Gruyter GmbH, 2014). b) J. C. Pastre, D. L. Browne, S. V. Ley, Chem. Soc. Rev. 2013, 42, 8849-8869. c) B. Gutmann, D.
Cantillo, C. O. Kappe, Angew. Chemie Int. Ed. 2015, 54, 6688–6728. d) C. Rodríguez-Escrich, M. A. Pericàs, Eur. J. Org. Chem. 2015, 1173-1188. e) J .
Britton, S. Majumdar, G. A. Weiss, Chem. Soc. Rev. 2018, 47, 5891-5918. 2. M. B. Plutschack, B. Pieber, K. Gilmore, P. H. Seeberger, Chem. Rev. 2017 ,
117, 11796–11893. 3. www.ertflow.com
38
ABSTRACTS
POSTERS
39
Poster 1
Jianing Xie
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
A Stereoselective Domino Approach towards α,β-Unsaturated γ-Lactams
Jianing Xiea, Sijing Xuea, Arjan W. Kleija,b*
a, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain,
b, Catalan Institute of Research and Advanced Studies (ICREA), Pg. Lluís Companys 23, 08010 Barcelona, Spain.
Small nitrogen-containing heterocycles are often found in important chemicals
such as natural products, pharmaceuticals and agrochemicals. Palladium-catalyzed nucleophilic amination of allylic species represents one of the most
efficient ways for the construction of new C‒N bonds. Direct amination of allylic alcohols using intermolecular activation has been developed as a green
and atom-economical process with water as the sole by-product. Despite notable progress in this area, direct aminolysis of allylic alcohols toward the
stereoselective preparation of multisubstituted allylic amines still presents a fundamental and practical challenge. Inspired by previous research in our group
concerning the stereoselective formation of (Z)-configured allylic products obtained from vinyl-substituted cyclic carbonates,[1] herein we describe a new
and attractive method for the amination of allylic alcohols under high stereocontrol (Figure 1). Key to this stereoselective transformation is the
presence of a carboxylic acid acting as a directing and activating group. The isolated α,β-unsaturated lactams represent useful heterocyclic scaffolds with
ample functional group diversity.[2]
References
1. For a general review: W. Guo, J. E. Gómez, A. Cristofol, J. Xie, A. W. Kleij, Angew. Chem. Int. Ed. 2018, 57, 13735.
2. J. Xie, S. Xue, E. C. Escudero-Adán, A. W. Kleij, Angew. Chem. Int. Ed. 2018, DOI:10.1002/anie.201810160.
40
Poster 2
Estefanía del Castillo
ICIQ - INTECAT School | Abstract
41
Poster 3
Núria Llorente
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
TOWARDS EFFICIENT METAL-CATALYZED [4+4]-CYCLOADDITION REACTIONS.
N. Llorente,a H. Fernández-Pérez,a A. Vidal-Ferran a,b,*
a Institute of Chemical Research of Catalonia & Barcelona Institute of Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain;
b ICREA, Pg. Lluís Companys 23, 08010 Barcelona, Spain
[email protected]; [email protected]
Higher-order cycloadditions constitute an extremely useful tool in organic
synthesis as they may generate complex molecular structures from readily accessible building blocks with high regio-, diastereo- and enantioselectivities
and high atom efficiency. This work reflects our efforts in the development of efficient catalytic methods for metal-mediated intramolecular [4+4]
cycloadditions of structurally diverse bisdiene substrates. In the seminal work of Wender et al.,1 Ni(0) complexes were reported to be efficient catalyst for this
type of transformations. The use of electron-rich triarylphosphines as ligands improves the selectivity in the formation of the target cyclic compounds. The
stereoselective formation of trans- and cis-fused eight-membered cyclic compounds was obtained starting from the adequate isomer of the bisdiene
substrate and rationalized by DFT computational studies (Scheme 1).2
References
1. P. A. Wender, N. C. Ihle, J. Am. Chem. Soc. 1986, 108, 4678 2. N. Llorente, H. Fernandez-Perez, A. Bauza, A. Frontera, A. Vidal-Ferran,
Catal. Sci. Technol. 2018, 8, 5251
42
Poster 4
M.B. Yeamin
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Transforming CO2 into Cyclic Carbonate Using Lignocellulosic Waste as Catalyst: Experimental and
Computational Approach
M. B. Yeamin1, A. Aghmiz2, M. Reguero1 and A. M. Masdeu1
1Universitat Rovira i Virgili, Departament de Química Física i Inorgànica, C.
Marcel·lí Domingo 1, 43007-Tarragona, Spain,
2Faculté des Sciences, University Abdelmalek Essaadi, Mhannech II, B.P.
2121, 93030 Tétouan, Morocco
Carbon dioxide has become an alternative feedstock to produce high value chemicals and polymers [1, 2]. The need of decreasing the greenhouse gas
emission in the atmosphere made the CO2 transformation a promising research area. The main drawback is its thermodynamic stability and kinetic inertness.
To overcome this problem the use of catalysts or highly reactive substrates is required. [3].
Scheme 1. Reaction profile of CO2 cycloaddition to propylene oxide catalyzed
by tetrabutyl ammonium chloride (TBAB)/Cellutriose (CtS) system. We present the catalytic performance of some lignocellulosic biomass wastes
such as residues from olives, sawdust, cereals and grapes in combination with nucleophiles, in the conversion of CO2 into cyclic carbonate. The mechanistic
study with Density Functional Theory (DFT) provides the molecular interpretation of the catalytic process (Scheme 1).
References [1] R. Rajagupal, Sustainable Value Creation in the Fine and Speciality Chemicals
Industry, John Wiley & Sons Ltd., 2014.
[2] M. Alves, B. Grignard, R. Mareau, C. Jerome, T. Tassaing, and C. Detrembleur,
Catal. Sci.Technol., 2017, 7, 2651.
[3] L. Cuesta-Aluja, A. Campos-Carrasco, J. Castilla, M. Reguero, A. M. Masdeu-
Bultó, A. Aghmiz, J. CO2 Utilization, 2016, 14, 10.
43
Poster 5
Raúl Pérez-Soto
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Understanding the self-assembly process of Imine Cages
Feliu Maserasa,b, Maria Besorac,Raúl Pérez-Sotoa*
a, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science
and Technology, 43007 Tarragona, Spain b, Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Spain.
c, Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, 43007 Tarragona, Spain,
Porous organic cages (POCs) are organic molecules with an accessible intrinsic pore1. Porous materials built from POCs are versatile and have a variety of
applications and properties. Imine cages are a family of POCs. They are generally formed in a one-pot synthesis between two monomers, one with
aldehyde groups and another with primary amines. In-silico design of these cages has relied either in pure thermodynamics, in experimental trial-error and
recently Cooper group used a hybrid approach2. Whereas some experimental work3 has attempted to understand the kinetics of this self-assembly process
there is much to learn yet. In order to gain insight into this process we have computationally studied the thermodynamics and kinetics of the synthesis of
the CC1 imine cage. We are constructing a reaction network connecting reactants and products. Scheme 1 shows the different parts of the studied
reaction network and has allowed to draw some interesting conclusions.
Scheme 1: Reaction types considered in the study
References 1. Chong S. Y. and Cooper A. I. in Comprehensive Supramolecular Chemistry,
Vol II, Elsevier, 2017, pp. 139–197. 2. Cooper A. I. et al, Nat. Commun., 2018, 9, 2849.
3. Zhu G. et al, Chem. Mater., 2017, 30, 262-272.
44
Poster 6
Mauro Mato
ICIQ - INTECAT School | Abstract
45
Poster 7
Vicente Dorado
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
CATALYTIC ROUTES FOR THE SYNTHESIS OF HIGH ADDED VALUE PRODUCTS FROM FATTY ESTERS
Vicente Doradoa*, José M. Frailea, Clara I. Herreríasa
a, Instituto de Síntesis Química y Catálisis Homogénea (ISQCH), CSIC-
Universidad de Zaragoza, C/ Pedro Cerbuna 12, Zaragoza, España. * [email protected]
The transformation of the hydrocarbonated chain of fatty acids has a great potential to obtain high added value products. For this reason, many reactions
on the C=C double bonds of insaturated fatty acids have been described in the literature1. An interesting example is the epoxidation2 because the epoxide can
be used for the preparation of ketones3, diols4 or alcohols5. In this communication catalytic sustainable methods for the preparation of high added
value products from methyl oleate are reported (Fig. 1). From the epoxidation of methyl oleate, the epoxide was used as starting material to obtain ketoesters,
hydroxyesters and the corresponding 1,2-diol. The oxidative cleavage of 1,2-diol allowed us to obtain a mixture of nonanoic acid and azelaic acid, without
the use of harmful reactives. In should be noted that in all processes an overall yield greater or equal than 80% was obtained.
Fig 1. Scheme of the catalytic routes from methyl oleate.
References 1.Metzger, J. O., Eur. J. Lipid Sci. Technol 2009, 111, 865-876.
2.Campanella, A.; Baltanás, M. A.; Capel Sánchez, M.C.; Campos-Martín, J. M. and G. Fierro, J.
L. Green Chem. 2004, 5, 330-334.
3.Doll, K. M.; Bantchev, G. B. and Murray, R. E., ACS Sustainable Chem. Eng. 2013, 1, 39-45.
4.Ahn, B. K.; Kraft, S. and Sun, X. S., J. Mater. Chem., 2011, 21, 9498-9505.
5.Howton, D. R. and Kaiser, R.W. Jr, J. Org. Chem. 1964, 29, 2420-2425.
46
Poster 8
Anna M. Sobolewska
Laura Amenós
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
INNOVATIVE SOLUTIONS IN CATALYSIS & FLOW PROCESSES FOR SUSTAINABLE CHEMISTRY
Anna M. Sobolewskaa*, Laura Amenósa*, Esther Alzaa, Miquel A. Pericàsa a, Institut Català d’Investigació Química, Avda. Països Catalans, 16, 43007,
Tarragona. * [email protected], [email protected]
Flow chemistry represents an alternative to the traditional ‘round-bottomed
flask’. Many advantages of flow devices have been presented, for instance improved heat and mass transfer, mixing time, easier scale-up and
reproducibility due to the better control over reaction conditions. The application of continuous flow chemistry concepts in the chemical and
pharmaceutical industry has gained great recognition in recent years. These processes provide solutions to complex problems, both in the synthesis of
molecules, and in the process optimization. In addition continuous processes can be easily integrated with other novel methodologies such as photo- and
electrochemistry, microwave irradiation, 3D printing or microreactors.1-3
ERTFLOW is a technology transfer unit of ICIQ that aims the development of efficient processes in continuous flow. ERTFLOW team has strong background
in organic synthesis and flow chemistry, along with extensive experience in the development of immobilized catalysts.4 Moreover, we provide custom
synthesis, design and development of safer, economical and easily scalable processes in continuous flow with industrial interest.5
ERTFLOW is a part of the FLOW4HEALTH project funded by the Spanish
Government. Our team together with Esteve and Esteve Química works on the development of new continuous flow processes for pharmaceutical industry.
This novel technology allows a rapid transition from the discovery phase to manufacturing of new molecular entities.
References
1. C. Wiles, P. Watts, Green Chem. 2014, 16, 55-62; Green Chem. 2012, 14, 38-54.
2. A. Adamo, et. al. Science 2016, 352, 61-67. 3. R. Porta, M. Benaglia, A. Puglisi, Org. Process Res. Dev. 2016, 20, 2-25. 4. C. Rodríguez-Escrich, M. A. Pericàs, Eur. J. Org. Chem. 2015, 1173-1188. 5. www.ertflow.com
47
Poster 9
Pedro Alonso
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Synthesis and Application of C2-Symmetric Chiral Bifunctional Triamines in Asymmetric Organocatalysis
Santiago Cañellasa, Pedro Alonsoa*, Miquel À. Pericàsa,b
a, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of
Science and Technology, Avda. Països Catalans 16, E-43007 Tarragona, Spain b, Departament de Química Inorgànica i Orgànica, Universitat de Barcelona,
Martí i Franquès 1-11, 08028 Barcelona, Spain
The synthesis and application of newly designed C2-symmetric chiral bifunctional triamines (C2-CBT) is reported.1 Inspired by the performance of
chiral vicinal diamines in the activation of carbonyl functionalities,2 the design of a new family of aminoacid-derived compounds was envisioned. These
enantiopure triamine scaffolds can be synthesized in a straightforward manner in multigram amounts while avoiding chromatographic purification. As a proof
of principle, C2-CBT have been studied as catalysts for the aldol reaction of cyclic ketones with isatins, enabling access to the corresponding tertiary
alcohols. Besides, catalyst recovery by simple extraction techniques and subsequent reuse has been demonstrated.
References
1. S. Cañellas, P. Alonso, M. A. Pericàs, Org. Lett. 2018, 20, 4806-4810. 2. S. Cañellas, C. Ayats, A. H. Henseler, M. A. Pericàs, ACS Catal. 2017, 7,
1383-1391.
CO2H
NH2 NH2 NH2
N
NH2
6 synthetic steps* modulable synthesis* multigram availability* recoverable catalysts* enhanced catalytic activity
C2-CBT
NO
O
R2 X
O
C2-CBT
NO
R2
HOX
O
R1
R1
up to 98% yield,ee=96%, dr=13:1
48
Poster 10
Shang-Zheng Sun
ICIQ - INTECAT School | Abstract
49
Poster 11
Vanesa Salamanca
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Pd-catalyzed direct arylation of pyridine assisted by
the ligand [2, 2’-Bipyridin]-6(1H)-one
Vanesa Salamanca and Ana C. Albéniz*. IU CINQUIMA/Química Inorgánica, University of Valladolid,Campus Miguel
Delibes, Paseo de Belén, 7, Valladolid, 47011, Spain. [email protected]
Palladium-catalyzed C-C coupling reactions that directly functionalize C-H bonds have recently emerged as a powerful method for C-C bond
formation. These reactions do not require a previous functionalization of every reagent and therefore conforms to the principles of green chemistry.
Direct arylation of pyridine has been reported using the catalytic system formed by [Pd(OAc)2] and o-phenanthroline as ligand, with good yields but
long reaction times.1 In this work we have carried out the direct arylation of pyridine using [Pd(bipy-6-OH)Br(C6F5)] (bipy-6-OH = [2,2'-bipyridin]-
6(1H)-one) as catalyst (Figure 1). The reaction times are considerably reduced by the use of this ligand. Other arenes such as benzonitrile,
methoxybenzene or toluene have also been arylated. Kinetic isotope effect experiments show that C-H activation is the rate limiting step of the
reaction but the chelate N-donor ligand bipy-6-OH, which has a basic keto group as substituent, facilitates it. The ligand assists the C-H cleavage by a
concerted mechanism in the metal sphere. Experimental results and computational studies show that this is the case, leading to a dramatic
shortening of reaction times (Figure 1). This will be discussed in detail.
Figure1.Direct arylation of pyridine catalyzed by [Pd(bipy-6-H)Br(C6F5)] and schematic CMD transition state.
Acknowledgements We are grateful to the Spanish MINECO (SGPI, grant CTQ2016-80913-P)
for financial support.
References 1. Ye, M.; Gao, G.L.; Edmunds, J.F.A.; Worthington, P.A.; Morris, J.A.;
Yu, J-Q. JACS, 2011, 133, 19090.
50
Poster 12
Giulio Goti
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Stereocontrolled Synthesis of 1,4-Dicarbonyl Compounds by Photochemical Organocatalytic
Acyl Radical Addition to Enals
Giulio Gotia*, Bartosz Bieszczada, Alberto Vega-Peñalozaa, Paolo Melchiorrea,b
a, ICIQ, Avenida Països Catalans 16, Tarragona b, IIT, via Morego 30, Genoa
Chiral 1,4-dicarbonyl compounds are versatile synthetic intermediates and
important frameworks encountered in pharmaceutical and natural products.1
Nevertheless, catalytic asymmetric methods to access these molecular
fragments in enantioenriched fashion are rare.2 A valuable approach to the synthesis of 1,4-dicarbonyl compounds is offered
by the ability of acyl radical intermediates to participate in conjugate additions with Michael acceptors.3 However, an enantioselective catalytic version of this
radical approach has not yet been achieved. Herein, we report a photochemical organocatalytic protocol4 that addresses this
deficit in enantioselective synthesis.5 Specifically, we exploited iminium ion-mediated catalysis to activate enals 2 and trigger the enantioselective
interception of photochemically generated acyl radicals to afford enantioenriched 1,4-dicarbonyls 3 (Figure 1). Visible-light excitation of 4-acyl-
1,4-dihydropyridines (acyl-DHPs, 1) provided the reactive acyl radicals under mild reaction conditions.
References 1. M. P. DeMartino, K. Chen, P. S. Baran, J. Am. Chem. Soc. 2008, 130, 11546.
2. a) H.-Y. Jang, J.-B. Hong, D. W. C. MacMilllan, J. Am. Chem. Soc. 2007, 129, 7004; b) S. R. Yetra, A. Patra, A. T. Biju, Synthesis 2015, 47, 1357.
3. L. Capaldo, R. Riccardi, D. Ravelli, M. Fagnoni, ACS Catal. 2018, 8, 304. 4. M. Silvi, P. Melchiorre, Nature 2018, 554, 4.
5. G. Goti, B. Bieszczad, A. Vega-Peñaloza, P. Melchiorre, Angew. Chem. Int. Ed. DOI:10.1002/anie.201810798.
51
Poster 13
Enric Petrus
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Photochemical generation of peroxouranates and H2
Enric Petrusa*, Mireia Segadoa, Nuno A.F. Bandeiraa, Joan González
Fabraa, Carles Boa,b a, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of
Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain.
b, Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel·lí Domingo s/n, 43007 Tarragona, Spain.
Burns’ group recently revealed a photochemical water oxidation reaction
involving uranyl nitrate.1 In fact, it has been shown that in basic conditions and sunlight irradiation both an uranyl peroxide complex and molecular hydrogen
are formed. Due to the fact that it is not a complete water oxidation, a further protonolysis must be carried out so as to obtain hydrogen peroxide and
regenerate the initial complexes. Even though it is not a catalytic reaction but a stoichiometric one, other groups have been attracted to explore this reactivity.
Actually, Cahill’s group applied this chemistry to prepare bipiridine peroxo-bridged clusters2 and Perleppes’ group used oxime ligands3. Nevertheless, littl e
is known about how the photochemical partial water oxidation process takes place and the hypothetically applicability of these clusters into catalysis.
Hitherto, we have studied the ground states of all the intermediates up to the hydroxide dimer. However, due to the fact that the uranyl peroxide is only
formed under sunlight, the reactivity in the excited state surfaces has been explored as well.
References 1. McGrail, B.T.; Pianowski, L. S.; Burns, P.C. J. Am. Chem. Soc. 2014,
136(13), 4797−4800. 2. Thangavelu, S. G.; Cahill, C. L. Inorg. Chem. 2015, 54 (9), 4208.
3. Tsantis, S. T.; Zagoraiou, E.; Savvidou, A.; Raptopoulou, C. P.; P sychari s , V.; Szyrwiel, L.; Hołyńska, M.; Perlepes, S. P. Dalton Trans. 2016, 45 (22),
9307
52
Poster 14
Guillem Peñuelas
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Efficient Hydrogen Bonding Recognition in Water using Aryl-extended Calix[4]pyrrole Receptors
Guillem Peñuelas-Haroa,b,*, Pablo Ballestera,c
a, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology (BIST), Av. Països Catalans, 16, 43007-Tarragona,
Spain.
b, Universitat Rovira i Virgili, Departament de Química Analítica i Química Orgànica c/Marcel·li Domingo, 1, 43007-Tarragona, Spain.
c, ICREA, Pg. Lluís Companys, 23, 08018-Barcelona, Spain. * [email protected]
We describe the synthesis of four water-soluble aryl-extended calix[4]pyrrole receptors and report their binding properties with multiple neutral polar guests
in water. The prepared receptors present functionalization at both upper and lower rims. We have previously demonstrate that upper1 and lower2 rims can be
functionalized to provide water solubility to the aryl-extended calix[4]pyrrole scaffolds. The four synthetized receptors have in common the placement of
water solubilizing pyridinium groups at their lower rims, based on their performance for solubilizing related resorcinarene derived cavitands in water.3
We investigate the interaction of the receptors with a guest series in water solution using 1H NMR titrations and ITC experiments. Despite the known
competitive nature of water for hydrogen-bonding interactions, we demonstrate the formation of thermodynamically highly stable 1:1 inclusion complexes
stabilized by hydrogen-bonding interactions (figure 1a). We show that increasing the hydrogen-bond acceptor character of the guest has a positive
impact on binding affinity. This result suggests that the receptor’s cavity is indeed better hydrogen-bonding donor to interact with the guests than water
molecules. We also assess the important contribution of the hydrophobic effect to binding by comparing the binding affinities of analogous inclusion
complexes in water and chloroform solutions (figure 1b). The more polar guests are bound with similar affinities in the two solvents. We compare the
binding properties of the different complexes in order to derive general trends.
53
Figure 1: a) Energy minimized estucture (MM3) of the 1:1 inclusion complex formed by
cavitand 1oo and δ-lactam. Lower rim and non-polar hydrogens have been removed for
clarity. b) Plot of ΔG vs H-bonding acceptor capabilities (β) for the inclusion complexes
of the five 6-membered cyclic guest with 1oo (squares, H2O dashed-line) and 17oo
(circles, CHCl3 solid-line) receptors.
References
1. B. Verdejo, G. Gil-Ramírez and P. Ballester, J. Am. Chem. Soc., 2009, 131,
3178-3179.
2. D. Hernandez-Alonso, S. Zankowski, L. Adriaenssens and P. Ballester, Org.
Biomol. Chem., 2015, 13, 1022-1029.
3. R. Pinalli, G. Brancatelli, A. Pedrini, D. Menozzi, D. Hernández, P. Ballester,
S. Geremia and E. Dalcanale, J. Am. Chem. Soc., 2016, 138, 8569-8580.
54
Poster 15
Cristina Maquilón
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Stereo/Regio-Divergent Synthesis with CO2
Cristina Maquilóna*, Víctor Lasernaa, Arjan Kleijab* a ICIQ/BIST, Av. Països Catalans 16, 43007 Tarragona, Spain
b ICREA, Pg. Lluis Companys 23, 08010 Barcelona, Spain
* [email protected], [email protected]
Carbon dioxide (CO2) offers a cheap and renewable carbon feedstock for fine-chemical synthesis.1 However, it remains a huge challenge to prepare densely
substituted/functionalized organic cyclic carbonate scaffolds. Stereoselective conversions represent a relatively new area in CO2 valorization catalysis. In this
respect, here the reactivity of the epoxy alcohols towards the stereocontrolled synthesis of cyclic carbonates has been studied employing bicyclic substrates
(Figure 1).2 New stereo- and regio-divergent potential has been uncovered, allowing to convert a single substrate selectively into multiple products.
This project has so far resulted in the unexpected formation of various
stereoisomers (i.e., of type 2) that cannot be formed via conventional pathways . Control experiments demonstrate a unique sequence of steps that depend on the
stereochemical configuration of the epoxy alcohol substrate, and importantly on the presence of an alcohol fragment.
References
1. Q. Liu, L. Wu, R. Jackstell, M. Beller, Nat. Commun. 2015, 6, 5933. 2. V. Laserna, E. Martín, E. C. Escudero-Adán, A. W. Kleij, ACS Catal. 2017, 7,
5478−5482.
55
Poster 16
Eric Cots
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Asymmetric Iodine(I/III)-Catalysed Diamination of Styrenes
Eric Cotsa*, Kilian Muñiza,b
a, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of
Science, Av. Països Catalans 16, 43007, Tarragona, Spain
b, ICREA, Passeig Lluís Companys 23, 08010 Barcelona, Spain
The recent development of chiral iodine (I/III) catalysis has enabled many
asymmetric transformations, particularly in the field of oxidation reactions1. The most notable catalyst design is based on a resorcinol core and the
attachment of two lactic side chains bearing ester or amide groups. This modular nature of the mentioned structures enables a privileged catalyst
synthesis as fine-tuning for the specific reaction requirement is straightforward2. This work, based on a previous iodine (III)-mediated
reaction3, focuses on an enantioselective catalytic diamination of alkenes by a chiral lactate-based aryliodine within the iodine (I/III) manifold. By the use of
mCPBA as terminal oxidant and under optimised conditions, the reaction proceeds under complete intermolecular reaction control to yield the
diamination of terminal and internal styrenes4.
References 1. a) S. Haubenreisser, T. H. Wöste, C. Martínez, K. Ishihara, K. Muñiz,
Angew. Chem. Int. Ed. 2016, 55, 413; b) T. H. Wöste, K. Muñiz, Synthesis 2016, 48, 81.
2. A. Flores, E. Cots, J. Bergès, K. Muñiz, Adv. Synth. Catal. 2019, 361, xx–xx. 3. C. Röben, J. A. Souto, Y. González, A. Lishchynskyi, K. Muñiz, Angew.
Chem. Int. Ed. 2011, 50, 9478. 4. K. Muñiz, L. Barreiro, R. Martín Romero, C. Martínez. J. Am. Chem. Soc.
2017, 139, 4354.
R
I
O ON
O O
N
Cat. (20 mol%), HNMs2, mCPBA
MTBE/HFIP (3/1, v/v), -5 ºC
NMs2
NMs2
56
Poster 17
A.Martínez-Carrión
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Variable Time Normalization Analysis for Kinetic Treatments of Supramolecularly regulated Asymmetric
Hydroformylation
A. Martínez-Carrión,a, Jordi Burés,b A. Vidal-Ferrana,c* a Institute of Chemical Research of Catalonia & The Barcelona Institute of
Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain. b The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
c ICREA, Pg. Lluïs Companys, 23, 08010 Barcelona, Spain.
[email protected]; [email protected]
Operando spectroscopy allows the real-time monitoring of a catalytic process using different spectroscopic techniques. There are scarce examples in the
literature where operando NMR spectroscopy has been applied to study high-pressure reactions.1 An experimental set up has been developed for operando
hydroformylation reactions monitoring 1H-NMR spectroscopy.
Variable Time Normalyzed Analysis (VTNA) is a simple graphical analysis
method which uses all the data provided by modern reaction monitoring techniques and enables the elucidation of the reaction order of each component,
as well as the kobs with a simple mathematical data treatment.2 The combination of operando NMR spectroscopy and VTNA has facilitate the
removal of kinetic effects such as induction periods and the elucidation of the reaction orders under catalytic conditions revealing kinetic information of the
supramolecularly-regulated hydroformylation reaction.3
References 1. A. C. Brezny, C. R. Landis, J. Am. Chem. Soc. 2017, 139, 2778-2785.
2. (a) J. Bures, Angew. Chem., Int. Ed. 2016, 55, 2028-2031. (b) J. Bures, Angew. Chem., Int. Ed. 2016, 55, 16084-16087.
3. Submitted manuscript.
57
Poster 18
Justine Raymond
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Enabling Technologies and Drug Discovery: Continuous Flow Processes to Discover Novel Antiviral Inhibitors Justine Raymonda, Elena Dettab, Tamás Vermesb, Esther Alzaa, Miquel
Pericasa, Alastair Donaldb, Andreas Urbanb, Thomas Goldnerb, Helmut Buschmannb
a, Institute of Chemical Reseach of Catalonia (ICIQ), Av. Països Catalans 16,
43007, Tarragona, Spain b, AiCuris Anti-infective Cures GmbH, Friedrich-Ebert-Str. 475 ,42117,
Wuppertal
The efficient production of drugs represents a challenge for society, including
the need of new molecular entities (NME) for the treatment of various diseases of high prevalence such as Hepatitis B.1 The fast and effective development of
NMEs requires the development of innovative and effective methodologies. In that sense, synthetic processes using continuous flow represent a novel area with
high potential.2 VIRO-FLOW project3 will focus its research on the fast and efficient identification of new, curative antiviral agents and innovative inhibitors
of the Hepatitis B Virus (HBV) integrating the advantages of continuous flow chemistry with in vitro microfluidic bioassay technologies. The project will
allow the preparation of a large number of NMEs, providing disruptive technology, generating advanced multidisciplinary knowledge in synthesis, flow
chemistry, microfluidics, in silico studies and bioassays in the antiviral field for all the ESRs, as well as for AiCuris and ERTFLOW Unit from ICIQ.
References
1. Paul, S. M.; Mytelka, D. S.; Dunwiddie C. T.; Persinger, C. C.; Munos, B. H.;
Lindborg, S. R.; Schecht, A. L. Nat Rev Drug Discov. 2010, 9, 203-241
2. a) Flow Chemistry (Eds.: F. Darvas, V. Hessel, G. Dorman), De Gruyter, Berlin, 2014. b) Microreactors in Preparative Chemistry (Ed.: W. Reschetilowski), Wiley-VCH,
Weinheim, 2013 3. www.viro-flow.eu - VIRO-FLOW has received funding from the European Union’s
Horizon 2020 research and innovation programme under grant agreement No 766058
Figure 1: Integrated system for generation of SAR data
58
Poster 19
Joan Saltó
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
A theoretically-guided optimization of a new family of modular P,S-ligands for Pd-catalyzed asymmetric allylic
substitution
J.Saltóa*, M. Bioscaa, J. Margalefa, X. Caldenteyb, M. Besorab, C.Rodríguez-
Escrichb, X. C. Cambeirob, F. Maserasb, O. Pàmiesa, M. Diégueza, M. A. Pericàsb.
aDepartament de Química Física I Inorgànica, Universitat Rovira i Virgili,
C/Marcel·lí Domingo, 1, 43007 Tarragona, Spain bInstitute of Chemical Research of Catalonia (ICIQ). The Barcelona Institute of
Science and Technology, Av. Països Catalans, 16 43007, Tarragona, Spain,
Allylic substitution is nowadays a valuable tool for organic synthetic chemistry. Nevertheless, most of the reported studies have shown low reaction rates, high
substrate specificity and a really short nuclephile scope.1 To overcome those limitations, the use of biaryl phosphite-containing ligands have shown to be
advanteageous.2 The use of P-thioether ligands have been dismished since high entantioselectivities have been achieved only with standard substrates.3
In collaboration with Profs. Pericàs and Maseras, we have gaven a new push to the study of the catalytic potential of P-thioether ligands. We synthesized a new
P-S ligand library in only three steps from inexpensive indene (Figure 1).
DFT calculations allowed the optimization of the ligand
parameters. We were therefore able to obtain excellent ee's in broad range
of substrates with a wide range of C-, N- and O- nucleophiles (40
compounds in total). We also used tandem reactions to show the versatility of this synthetic methodology.4
References 1 L. Milhau, P.J. Guiry, Top Organomet Chem. 2012, 38, 95–154 and references there in. 2 M. Diéguez, O. Pàmies. Acc. Chem. Res., 2010, 43, 312–322 and references there in. 3 R. G. Arrayás, J. C. Carretero, Chem. Commun. 2011, 47, 2207-2211 and references there in. 4 M. Biosca, J. Margalef, X. Caldentey, M. Besora, C. Rodríguez-Escrich, J. Salto, X. C. Cambeiro, F. Maseras, O. Pàmies, M, Diéguez, M. A. Pericàs, ACS Catal.,
2018, 8, 3587-3601.
Figure 1. P-S ligands for allylic substitution.
59
Poster 20
Helena Armengol-Relats
ICIQ - INTECAT School | Abstract
60
Poster 21
Bruna S. Pladevall
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Insights into mechanochemical reactions: Is it possible to reproduce them computationally?
Bruna S. Pladevalla*, Feliu Maserasa,b
a, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of
Science and Technology,Av. Paisos Catalans, 16, 43007 Tarragona, Spain. b, Departament de Química, Universitat Autónoma de Barcelona, 08193
Bellaterra, Spain.
Mechanochemical reactions are those induced by mechanical means (milling,
grinding or compression) and conducted either in solvent-free conditions or using solvent in very small amounts.1 The overall necessity of greener synthetic
paths has resulted in an increased investigation on mechanochemical routes. Still, the underlying processes are not well understood. Herein we implement a
combination of DFT tools and kinetic studies on two selected reactions: the synthesis of N-sulfonylguanidines2 (Figure 1, A) and a set of Diels-Alder
reactions3 (Figure 1, B), in order to rationalize their reaction outcome. We conclude that when a proper media and concentration corrections are
introduced, reaction mechanisms for mechanochemical reactions are comparable to those in solution.
Figure 1: Reactions included in the study. A, N-sulfonylguanidines synthesis and B, a set of Diels-
Alder reactions.
References
1. Do, J.L.; Friščić, T. ACS Cent. Sci. 2017, 3 (1), 13. 2. Tan, D.; Athanassios, C.M.; Katsenis, D.; Trukil, V.; Friščić, T. Angew.
Chem. Int. Ed. 2014, 53, 9321. 3. Andersen, J.M.; Mack, J. Chem. Sci. 2017, 8, 5447.
61
Poster 22
Patricia Llanes
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Organocatalytic Enantioselective Continuous-Flow Cyclopropanation
Patricia Llanesa, Carles Rodriguez-Escricha*, Sonia Sayaleroa, and Miquel
Pericása,b* a, Institute of Chemical Reseach of Catalonia (ICIQ), the Barcelona Institute of Science and Technology, Av. Països Catalans,16, 43007 Tarragona, Spain. b, Departament de Química Inorgánica i Orgánica, Universitat de Barcelona
(UB), 08028 Barcelona, Spain. [email protected]
A set of six solid-supported Jørgensen-Hayashi-type catalysts has been prepared
and applied to the enantioselective cyclopropanation of a,b-unsaturated aldehydes in flow. Different strategies have been used for preparation of the polymer matrix: copolymerization in suspension (leading to a microporous
resin1) and copolymerization in the presence of a porogen in a closed tubular reactor (leading to macroporous structures known as monoliths2). The optimal
candidate resin allowed the implementation of a long flow experiment (48 h) without significant deactivation. A similar continuous flow setup was used to
prepare a small library of 12 analogues by sequential flow experiment. The mildness and utility of the method have enabled a telescoped process in which
the outsream is directly used in a Wittig flow reaction (Scheme 1)3.
Scheme 1: Cyclopropanation of a, b-unsaturated aldehydes.
References
1. a) Fan, X.; Rodríguez-Escrich, C.; Sayalero, S.; Pericàs, M. A. Chem. -Eur. J. 2013, 19, 10814. b) Fan, X.; Rodríguez-Escrich, C.; Sayalero, S.; Pericàs, M. A.
Chem. -Eur. J. 2014, 20, 13089. 2. Aranda, C.; Cornejo, A.; Fraile, J. M.; García-Verdugo, E.; Gil, M. J.; Luis, S.
V.; Mayoral, J. A.; Martínez-Merino, V.; Ochoa, Z.; Green Chem. 2011, 13, 983-990.
3. Llanes, P.; Rodríguez-Escrich, C.; Sayalero, S.; Pericàs, M. A. Org. Lett. 2016, 18, 6292-6295.
NH
O
OTBS
PhPh
OHC
R
+CO2MeMeO2C
Br
CHO
MeOOC
MeOOC
R
*Asymmetric Flow Cyclopropanation
*Monolith vs Resin
*One 48 h long Flow Experiment
*Library of 12 Examples in Flow
(Total operation time: 76 h)
Ph3PCO2Et
MeOOC
MeOOC
R
CO2Et
62
Poster 23
R. Martin-Montero
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Ni-Catalyzed Reductive Cross-Electrophile Coupling of Alkyl Amines with Aryl Bromides
R. Martin-Montero, H. Yin, R. Yatham, R. Martin*
Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of
Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain.
ICREA, Passeig Lluïs Companys, 23, 08010 Barcelona, Spain
[email protected]; [email protected]
Prompted by the inherent toxicity and the availability of organic halides,
chemists have been challenged to design alternative counterparts for cross-coupling reactions. Among various scenarios, particularly attention has been
devoted to the utilization of simple alcohols or amine electrophiles via formal C-O and C-N cleavage.1 Taking into consideration the ubiquity of amines in a
myriad of molecules of utmost biological relevance,2 particularly attractive would be the means to promote late-stage functionalization of simple amines as
organic halide surrogates in cross-coupling reactions. Driven by the work of Watson with stoichiometric organometallic reagents3 as well as our continuing
interest in cross-electrophile coupling reactions,4 we present herein the feasibility of using simple amine derivatives in these endeavours, thus
constituting a strategic different approach to conventional C–C bond-formation. The protocol exhibits a broad applicability to a range of aryl and amine
counterparts, including the viability to trigger late-stage functionalization reactions.
References
1. C-O bond-cleavage reactions: Zarate. C.; Van Gemmeren. M.; Somerville. R. J.; Martin. R. Advances in Organometallic Chemistry, Elsevier, 2016,
66, 143-222. C-N bond-cleavage processes: Maity. P.; Shacklady-McAtee. D. M.; Yap. G. P. A.; Sirianni. E. R.: Watson M. P. J. Am. Chem. Soc.
2013, 135, 280-285. 2. (a) Ruiz-Castillo, P.; Buchwald, S. L. Chem. Rev. 2016, 116, 12564.
3. Basch. C. H.; Liao. J.; Xu. J.; Piane. J. J.; Watson. M. P. J. Am. Chem. Soc. 2017. 139. 5313-5316.
4. Serrano. E.; Martin. R.; Angew. Chem. Int. Ed. 2016, 55, 11207-11211.
Br
R1+
R3
R2NR1
R3
R2R2 Ni catalyst
Excellent yields&
broad scope
63
Poster 24
Ana Mateo
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Computational Study of Boron Insertion Reaction
into Benzofuran’s C-O Bond
Ana Mateoa*, Carles Boab
a, Catalonia Institute of Chemical Research (ICIQ), The Barcelona Institute of Science and Technology (BIST), Avinguda dels Països Catalans 16, 43007
Tarragona, Spain, b, Departament de Química Física i Inorgànica, Universitat Rovira i Virgili,
Carrer Marcel•lí Domingo 1, 43007 Tarragona, Spain.
Products of borylation reaction are important for organic synthesis, functional materials and bioagents1. Recently, Yorimitsu and coworkers2 presented a
boron insertion reaction into the C-O bond of benzofuran. This reaction is catalysed by Ni(0) complex bearing a NHC ligand in the presence of Cs2CO3.
In the classical transmetalation-like mechanism, the role of the salt is not clear, neither it is clear the sequence of the reaction steps.
In this communication, we present the results of a computational study carried out using DFT based methods (B3LYP-D3, M062X, and ωB97XD). We have
found that the reaction follows a cross-coupling like mechanism (Figure1). Also, we have proved the formation of the B2nip2-Cs2CO3 adduct.
Furthermore, the most favourable reaction path is the one where there is a boron insertion into Ni-C bond which results from the oxidative addition. And
then, the B-O bond formation gives the desired product directly. The reactivity of other substrates is explored.
References 1. See chapter 12, chapter 13 and chapter 14, in Boronic Acids, Vol 2:
Preparation and Applications in Organic Synthesis, Medicine and Materials, 2nd Edition, Hall, D. G., Ed. Wiley-V C H Verlag Gmbh: Weinheim, 2011; pp
551-590; pp 591-620; pp 621-676. 2. Saito, H.; Otsuka, S.; Nogi, K.; Yorimitsu, H., JACS 2016, 138 (47), 15315-
15318.
NiN
N
iPr
iPr
NiO
N
N
iPr
iPr
1-Ni
1-Ni-B
Int1-B-C
BO
O
O
2
O
1
B B OO
OO O O
O
AdductCs
Cs
B B
O
OO
O
O O
OCsCs
BO
O O
OO
+
O
BO O
Ni
N
NiPr
iPr
NiO
B
O
O
N
NiPr
iPr
*
*
*
*
64
Poster 25
María Pérez-Iglesias
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
“[Cu(C6Cl2F3)(tht)]”: Synthesis, Behaviour in Solution, and Reactivity as Arylating Reagent
María Pérez-Iglesias, Olmo Lozano-Lavilla, Isabel Arranz-delaCalle,
Juan A. Casaresa*
a, I.U. Cinquima. Paseo de Belén Universidad de Valladolid. 47011 Valladolid, Spain,
In recent years, the synthetic utility of organocopper compounds and their use
in catalysis has experienced an enormous growth.1 One of the fundamental roles of organocopper derivatives is the transmetalation in multimetallic
catalytic systems, such the Sonogashira cross-coupling or the copper assisted Hiyama reaction.2,3 The mechanistic study of these reactions has been
hampered by the extraordinary intrinsic reactivity and the structural complexity of organocopper complexes, to the point that nowadays there are no
experimental data about the species actually involved in the transmetalation, nor about the dependence of the reaction on the auxiliary ligands at the copper.
Aiming at studying the aryl transmetalation from aryl-copper complexes to other metals we have prepared the complex of molecular formula
“[Cu(C6Cl2F3)(tht)]”, containing a fluoroaryl ring in which the 19F nuclei do not show any JF-F coupling, which facilitates to obtain accurate kinetic data from
their 19F NMR spectra. In this communication we report the synthesis of this complex, its X-ray structure, the NMR study of its behaviour in solution
through DOSY experiments, and its reactivity as arylating reagent towards other metals.
References
1. N. Yoshikai, E. Nakamura, Chem. Rev. 2012, 112, 2339–2372.
2. R. Chinchilla, C. Nájera, Chem. Rev. 2007, 107, 874–922. 3. J. Delpozo, J. A. Casares, P. Espinet, Chem. - A Eur. J. 2016, 22, 4274–4284.
65
Poster 26
Catherine M. Holden
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Photo-Organocatalytic Enantioselective Radical Cascade Reactions of Unactivated Olefins
Pablo Bonilla,a Yannick P. Rey,a Catherine M. Holden,a* and Paolo
Melchiorrea, b a, Institute of Chemical Research of Catalonia (ICIQ), Av. Països Catalans 16,
43007, Tarragona, (Spain).
b, Italian Institute of Technology (IIT), Via Morego 30, 16163 Genoa (Italy). * [email protected]
Cascade processes are powerful strategies for rapidly increasing structural and stereochemical complexity while delivering complex chiral molecules in one
step. Recently, our laboratories identified a new photochemical catalytic mode of activation that exploits the excited-state reactivity of chiral iminium ions I to
generate radicals upon SET oxidation of suitable redox active substrates (Figure 1a).1 Presented in this work is a method for converting unactivated
alkenes and α,β-unsaturated aldehydes into chiral adducts in a single step (Figure 1b).2
Figure 1. Enantioselective cascade reaction triggered by the excitation of chiral iminium
ions with visible-light.
References 1. M. Silvi, C. Verrier, Y. P. Rey, L. Buzzetti, P. Melchiorre, Nat. Chem. 2017, 9, 868 –
873. 2. P. Bonilla, Y. P. Rey, C. M. Holden, P. Melchiorre Angew. Chem. Int. Ed. 2018, 5 7 , 12819 – 12823.
66
Poster 27
Adiran de Aguirre
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Computational analysis of the electronic structure a Fe(II) complexes bearing a new SMeNHS ligand
Adiran de Aguirrea*, Feliu Maserasa,b
a, Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of
Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Catalonia, Spain,
b, Departament de Química, Universitat Autònoma de Barcelona, 08193
Bellaterra, Catalonia, Spain * [email protected]
The structural and electronic characterization of organometallic complexes is
fundamental to understand their behaviour and reactivity. Computational
chemistry can be helpful in this concern.
In this work, we report computational (DFT) studies on the intriguing
electronic structure of a mononuclear Fe(II) complex bearing the new
monoanionic SMeNHS ligand1 and its structural and magnetic change upon
reaction with different ligands as P(OMe)3 or CO(Figure 1). The computational
results are in total agreement with the experimental data reported by Baker’s
group.
Figure 1. Derivatization of initial complex upon reaction with P(OMe)3 (right) and CO (left).
References
1 U.K. Das, S.L. Daifuku, S.I. Gorelsky, I. Korobkov, M.L. Neidig, J.J. Le Roy, M. Murugesu, R.T. Baker, Inorg. Chem. 2016, 55, 987-997.
67
Poster 28
Andreu Tortajada
ICIQ - INTECAT School | Abstract
68
Poster 29
Morgane Gaydou
Fernando Bravo
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Valorization of projects at CSOL: a scalable route to polymer-supported TRIP
Morgane Gaydoua, Fernando Bravoa*
a, CSOL unit: Institute of Chemical Research of Catalonia (ICIQ), Av. Països
Catalans 16, 43007 Tarragona * [email protected]
The unit CSOL of ICIQ acts as the institute’s valorization and innovation
laboratory. In this sense, CSOL has undertaken the scale up of processes discovered at ICIQ that can be of interest for the industry, the development
ICIQ’s technologies, or the construction of prototypes. As an example of our achievements, we present herein a scalable route towards
polymer-bouded TRIP organocatalyst. With respect to the original published route,1 this new synthesis avoids the use of chromatography or extreme
temperature conditions in all the reaction steps. Besides, it conveniently allows isolation of the expensive homogeneous TRIP organocatalyst2 as reaction
intermediate.
References 1. L. Clot-Almenara, C. Rodríguez-Escrich, L. Osorio-Planes, M. A. Pericàs ACS
Catal. 2016, 6, 7647-7651. 2. Compare the cost at Sigma Aldrich (€2.630,00/g) with our production costs
(including time) of €100,00/g.
69
Poster 30
Giuseppe Zuccarello
ICIQ - INTECAT School | Abstract
70
Poster 31
Benedetta Palucci
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Pd-catalyzed hydroformylation using formaldehyde as
syngas surrogates
Benedetta Palucci,a Carmen Claver, a,b Cyril Godard,b Jorge Sánchez Quesada,c and Sergio Castillón.b
a Centre Tecnològic de la Química,Tarragona, Spain.
b Departament de Química Física i Inorgánica, Universitat Rovira i Virgili,
Tarragona, Spain. c International Flavors & Fragrances Inc., Avda Felipe Klein, Benicarló, Spain.
The hydroformylation of alkenes is an iconic industrial applications of ho mogen eo us catalysis due to the added-value of the resulting aldehydes.[1] Although this process has
undergone continuous growth since its invention, it still mainly re li e s o n th e u se o f expensive transition-metal catalysts such as those based on rhodium and ruthenium an d the dangerous use of syngas. In contrast, palladium has not been appropriately exploited
in the area of hydroformylation since catalysts based on this metal originally targeted the formation of alternating polyketones from olefins with carbon monoxide, or
esters/carboxylic acids in the presence of methanol or water as nucleophiles.[2] Although some studies have focused in the use of palladium in hydrofromylation, o nl y recently it has been reported a Pd-catalytic system which delivers exclusively the linear
aldehyde, compared to other methods in which the branched regioisomer is observed.[3] Here we present a new approach to catalyse the hydroformylation of alkenes by palladium employing formaldehyde as syngas surrogates.[4] A mechanism, su pp or t ed
by 1H-NMR and GC studies, explaining the exclusive formation of the linear aldehydes is also proposed. This strategy is attractive as it utilizes highly available ch emi cals , a cheap and abundant metal for making added value molecules, avoiding the use of mo re
dangerous syngas.
Figure 1. Pd-catalysed hydroformylation using formaldehyde as syngas surrogate.
References
1. a) A. F. R. Börner, Hydroformylation: Fundamentals, Processes and Applications i n Organic Synthesis, 2016; b) M. Taddei, Mann, A., Hydroformylation for Organic Synthesis, 2013; c) F. Ungvári, Coord. Chem. Rev. 2007, 251, 2072-2086; d) P . W . N .
M. K. van Leeuwen, P. C. J.; Claver, C.; Pàmies, O.; Diéguez, M. , Chem. Rev. 2011, 111, 2077-2118. 2. a) J. Pospech, Fleischer, I., Franke, R., Buchholz, S., and Beller, M., Angew. Chem.
2013 , 52, 2852-2872 ; b) B. H. M. Drent E., Chem. Rev. 1996 , 96, 663-681 ; c) I. del Río, C. Claver, P. W. N. M. van Leeuwen, Eur. J. Inorg. Chem. 2001, 2719-2738. 3. W. C. Ren, W.; Dai, J.; Shi, Y.; Li, J.; Shi , Y. , J. Am. Chem. Soc. 2016 , 14864-
14867. 4. B. Palucci, , C. Claver, C. Godard, J. S. Quesada, S. Castillón. Manuscript in preparation.
71
Poster 32
Marconi N. Peñas-Defrutos
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
RhIAr/AuIAr' Transmetalation, a Case of Group Exchange Pivoting on Formation of M–M' Bonds via
Oxidative Insertion
Marconi N. Peñas-Defrutosa, Camino Bartoloméa, Max García-Melchorb, Pablo Espinet*a
a, I. U. CINQUIMA/Química Inorgánica, Universidad de Valladolid, Paseo de Belén 5, 47011, Valladolid, Spain
b, School of Chemistry, Trinity College Dublin, College Green, Dublin 2, Ireland.
Recently, we reported some complete mechanistic studies of different transmetalation reactions in bimetallic systems as PdII/AuI,1 or AuI/SnIV.2 In
some cases added ligand has not obvious effect on the reaction rate,1 or an apparently minute variation in the reactans provokes a dramatic mechanistic
change.2 In this context, we investigated the poorly studied RhI/AuI pair. The reversible Pf/Rf (C6F5/C6Cl2F3) exchange between [AuPf(AsPh3)] and
trans-[RhRf(CO)(AsPh3)2] (Scheme 1) does not take place by concerted aryl transmetalation via electron defficient double bridges, but involves oxidative
insertion of the RhI complex into the (AsPh3)Au–Pf bond producing a [(AsPh3)Au–RhPfRf(CO)(AsPh3)2] intermediate, followed by dissociation,
isomerisation and reductive elimination of [AuRf(AsPh3)]. Interesting differences are found between this LAu–Ar oxidative process and the classical
oxidative addition reaction of H–H to Vaska's complexes. Combined results from kinetic experiments, DFT calculations and COPASI
simulations, allows us to propose a complete mechanism for this transmetalation reaction.
Scheme 1
References 1. M. H. Pérez-Temprano, J. A. Casares, A. R. de Lera, R. Álvarez and P.
Espinet, Angew. Chem. Int. Ed. 2012, 51, 4917–4920. 2. D. Carrasco, M. García-Melchor, J. A. Casares and P. Espinet, Chem.
Commun. 2016, 52, 4305–4308.
72
Poster 33
Bertrand Schweitzer-Chaput
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Photochemical generation of radicals from alkyl electrophiles using a nucleophilic organic catalyst
Dr. Bertrand Schweitzer-Chaputa*, Dr. Matthew A. Horwitza, Eduardo de
pedro Beatoa, Prof. Paolo Melchiorrea,b
a, ICIQ, Av. Països Catalans 16 – 43007 Tarragona (Spain). b, IIT, via Morego 30 – 16163 Genoa (Italy)
The field of radical chemistry has experienced a recent revival thanks to the
emergence of photoredox catalysis, which allows the generation of radical intermediates under mild conditions.1 Here we report a novel photochemical
catalytic strategy to generate radicals from a variety of typically unreactive electrophilic compounds. We use a nucleophilic dithiocarbamate anion catalyst,
adorned with a well-tailored chromophoric unit, to activate alkyl electrophiles via an SN2 pathway. The resulting photon-absorbing intermediate affords
radicals upon homolytic cleavage induced by visible light.2
Unlike previous stoichiometric strategies using dithiocarbonyl compounds as stoichiometric reagents,3 we could achieve catalysis by designing suitable turn-
over events to regenerate the catalytically active anion under reaction conditions. The concept of dithiocarbamate anion catalysis was applied to
several transformations, including radical conjugate additions, alkylations of (hetero)aromatic substrates, asymmetric α-alkylation of aldehydes and the
functionalization of complex bioactive substrates.
References 1. C. K. Prier, D. A. Rankic, D. W. C. MacMillan, Chem. Rev. 2013, 113,
5322-5363. 2. Schweitzer-Chaput, B., Horwitz, M., De Pedro Beato, E., Melchiorre, P;
Nature Chem., 2018, Manuscript Accepted. 3. Quiclet-Sire, B.; Zard, S. Z. Chem. Eur.J. 2006, 12, 6002
73
Poster 34
Aijie Cai
ICIQ - INTECAT School | Abstract
74
Poster 35
Anastasia Tkacheva
ICIQ - INTECAT School | Abstract
75
Poster 36
Eric Tan
ICIQ - INTECAT School | Abstract
ICIQ - INTECAT School | Abstract
Chelation-Assisted Metal-catalyzed Alkynylation of C(sp2)-H Bonds
E. Tan,1 O. Quinonero,1 A. Konovalov,1 R. Dorel,1 G. A. Fernández,1 A. M.
Echavarren1,2 1 Institute of Chemical Research of Catalonia (ICIQ), Barcelona Institute of
Science and Technology, Av. Països Catalans 16, 43007 Tarragona, Spain. [email protected]
2 Departament de Química Analítica i Química Orgànica, Universitat Rovira i Virgili, C/Marcel·li Domingo s/n, 43007 Tarragona, Spain.
The aryl-alkyne bond is widely present in natural products, drugs, or organic materials and the alkynyl-substituent often imparts interesting properties.1 The
Sonogashira reaction is the most widely used method to construct the aryl-alkyne bond. However, in recent years, a complementary strategy emerged
based on transition metals catalysts which are able, upon coordination to a directing group, to cleave C(sp2)-H bonds and forge aryl-alkyne bonds (Scheme
1).2 Typical directing groups are amide functional groups, which need to be installed and then removed, thus lowering the step- and atom-economy when
used in synthesis. Our work aims to expand the scope of C-H alkynylation of (hetero)arenes, by developing reactions using instead widely used functional
groups as directing groups, such as phenolic –OH, carboxylic acid, ester and ketone.
Scheme 1. Construction of aryl-alkyne bonds via directed C-H activation.
References
1. A. Broggi, I. Tomasi, L. Bianchi, A. Marrocchi, L. Vaccaro, ChemPlusChem, 2014, 79, 486- 507.
2. a) R. Boobalan, P. Gandeepan, C.-H. Cheng, Org. Lett. 2016, 18, 3314-3317 b) Z. Ruan, N. Sauermann, E. Manoni, L. Ackermann, Angew. Int. Chem. Ed.
2017, 56, 3173-3176. c) S. H. Kim, J. Yoon, S. Chang, Org. Lett. 2011, 13, 1474-1477.
Directed C-H alkynylation
R
DGDG
H
Construction of aryl-alkyne bonds by C-H activation:
DG =OH
O O
OMe
O
Synthetically useful
OH
Widely used functional groups as directing groups: