Chemistry Letters · + R1 R2 – CO2 1,3-acyl migration N N O O R R1 R2 R1 R2 R Ni(0)/PCyp3...
8
Chemistry Letters http://www.csj.jp/journals/chem-lett/ Vol.40 No.4 CMLTAG April, 2011 ISSN 0366-7022 Copyright © 2011 The Chemical Society of Japan Highlight Review 330 Renaissance of Organic Synthesis Using Isocyanides Lewis acids Bronsted acids Transition-metal complexes cycloaddition insertion C-H bond functionalization heterocycle synthesis R N C Mamoru Tobisu and Naoto Chatani* doi:10.1246/cl.2011.330 New reactions using old functionality, isocyanides, are described. By using isocyanides inplace of carbon monoxide, transformations otherwise difficult to achieve, such as GaCl 3 -catalyzed [4 + 1] cycloaddition and TfOH-catalyzed insertion into a C-O bond of acetals, are realized. In addition, isocyanides are exploited as a key component in transition-metal-catalyzed C-H bond activation and borylation reactions. 341 Platinum Metals in the Catalytic Asymmet- ric Isomerization of AllylicAlcohols R 2 OH R 1 R 2 O R 1 R 3 R 3 H/R 4 H/R 4 Rh Ru Ir Luca Mantilli and Clément Mazet* doi:10.1246/cl.2011.341 Past and recent advances in the metal-catalyzed asymmetric isomerization of allylicalcohols into carbonyl compounds are discussed in the present Highlight. Emphasis isplaced on rhodium, ruthenium, and iridium; the only three metals that have proven successful to date for this most challenging transformation.
Transcript of Chemistry Letters · + R1 R2 – CO2 1,3-acyl migration N N O O R R1 R2 R1 R2 R Ni(0)/PCyp3...
Chemistry Lettershttp://www.csj.jp/journals/chem-lett/
Vol.40 No.4 CMLTAGApril, 2011 ISSN 0366-7022
Copyright © 2011 The Chemical Society of Japan
Highlight Review
330 Renaissance of Organic Synthesis UsingIsocyanides
Lewis acidsBronsted acidsTransition-metal complexes
cycloadditioninsertionC-H bond functionalizationheterocycle synthesis
RNC
Mamoru Tobisu and Naoto Chatani*doi:10.1246/cl.2011.330
New reactions using old functionality, isocyanides, are described. By using isocyanides in place of carbon monoxide,transformations otherwise difficult to achieve, such as GaCl3-catalyzed [4 + 1] cycloaddition and TfOH-catalyzed insertion into aCO bond of acetals, are realized. In addition, isocyanides are exploited as a key component in transition-metal-catalyzed CH bondactivation and borylation reactions.
341 Platinum Metals in the Catalytic Asymmet-ric Isomerization of Allylic Alcohols
R2 OH
R1
R2 O
R1
R3 R3
H/R4 H/R4Rh
Ru
Ir
Luca Mantilli and Clément Mazet*doi:10.1246/cl.2011.341
Past and recent advances in the metal-catalyzed asymmetric isomerization of allylic alcohols into carbonyl compounds arediscussed in the present Highlight. Emphasis is placed on rhodium, ruthenium, and iridium; the only three metals that have provensuccessful to date for this most challenging transformation.
345 Hydrogen Generation Using a PhotoinducedElectron-transport System with a MolecularCatalyst in Vesicles
Kentaro Watanabe, Shin-ya Takizawa, andShigeru Murata*doi:10.1246/cl.2011.345Electronic Supporting Information
Letter
348 Alkali Metal Ion Sensing Using AbsorbanceChanges Based on Aggregation of SilicaNanoparticles Modified Chemically withCrown Ethers
OH
SiO2
OHOHHO
O
HO
HO Si
(CH2)3
Me
O Si
Cl
(CH2)3
Me
O H
OO
O
N
O
x y
Crown-SNP
Yoshio Nakahara, Takafumi Hayashi, HarunaKawa, and Keiichi Kimura*doi:10.1246/cl.2011.348
351 Efficient Mannich Reaction Using IminiumSalts Generated from Glycine Derivatives
Makoto Shimizu,* Toshiki Kusunoki, MariYoshida, Koichi Kondo, and Isao Mizotadoi:10.1246/cl.2011.351Electronic Supporting Information
354 Photocatalytic Mineralization of Acetic Acidin Aqueous Suspension of Metal-loadedCerium(IV) Oxide under Irradiation ofVisible Light Pt/CeO2
Ag/CeO2
Cu/CeO2
CeO2
TiO2
Pt/TiO2
Acetic acid → CO2
0
2
4
6
8
10
12
0 5 10 15 20 25 30
CO
2 e
volv
ed /
µmol
Time / h
Atsuhiro Tanaka, Keiji Hashimoto, and HiroshiKominami*doi:10.1246/cl.2011.354
357 Bismuthtriflate-catalyzed Reaction of N-Alkylisatins with Allyltrimethylsilane
NO
O
R
R1
R2
SiMe3
R3
NO
R
R1
R2
HO
R3
+
1R = H, CH3, Et, Bn
R1 = H, CH3, F, Cl, Br, NO2, OCH3
R2 = H, Br R3 = H, CH3
5 mol% Bi(OTf)3·4H2O
THF, -78°C - 20°C
3
R5
R4 = R5 = H, CH3
R4
R5
R4
2
Harhadas M. Meshram,* Palakuri Ramesh, B.Chennakesava Reddy, and G. Santosh Kumardoi:10.1246/cl.2011.357Electronic Supporting Information
Chemistry Letters Vol.40, No.4 (2011)C-34
http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan
360 Preparation of Pure LiPF6 Using FluorineGas at Room Temperature
These figures show the IR spectrum (a) of gas products obtained at −20 °C and XRD profile (b) of LiPF6 product obtained through reaction between LiF and P in F2 gas at 23 °C. These results show new synthesis method of pure LiPF6 using fluorine gas at room temperature.
9001100130015001700Wavenumber/cm-1
Abs
orba
nce
10 20 30 40 50 60
1kcp
s (003
)(1
01) (012
)
(113
)
(024
)
(116
)
PF5
LiF(s) + P(s) + F2(g) ⇒ LiF(s) + PF5(g) ⇒ LiPF6
-20°C 23°C
(a) (b)
/degreeθ2
Jae-Ho Kim,* Hayato Umeda, Meguru Ohe,Susumu Yonezawa, and Masayuki Takashimadoi:10.1246/cl.2011.360
362 Mechanism of Heme Uptake by HemeAcquisition System A
Shin-ichi Ozaki,* Akira Nakahara, andTakehiro Satodoi:10.1246/cl.2011.362Electronic Supporting Information
364 Wittig Like Methylenation of Aldehydes in aMicroflow System: Selective Methylenationby Differential of Plural Reactions
CH2(ZnI)2
−1
−1
CHO
R1
CH=CH2
OHCOHC
0.55 M in THF
0.55 M in THF sat. NH4Cl aq
3.9 mL min
3.9 mL min
φ
φ
= 250 µm M1
= 1000 µmL = 0.5 m
61%Yoshiaki Takada and Seijiro Matsubara*doi:10.1246/cl.2011.364
366 Surface Segregation of Well-defied N-Sub-stituted Hyperbranched Polyamides in Lin-ear Polymer Matrix
Tomoyasu Hirai, Liu Huan, Yoshihiro Ohta,Tsutomu Yokozawa, and Keiji Tanaka*doi:10.1246/cl.2011.366
368 Practical Synthesis of Diethyl Phenylsucci-nate by Mg-promoted Carboxylation ofEthyl Cinnamate
XAr∆ / Dioxane
X = CO2Et, CN, COMeTotal Yield 38 ~ 71%
1) Mg / TMSCl / CO2 / DMF
2)X
COOEt
Ar
EtOH / H2SO43)Hirofumi Maekawa,* Taro Murakami, TakeshiMiyazaki, and Ikuzo Nishiguchi*doi:10.1246/cl.2011.368Electronic Supporting Information
Chemistry Letters Vol.40, No.4 (2011) C-35
http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan
370 Effective Depolymerization of Nylon-6 inWet Supercritical Hydrocarbons
NH
O
n
sub- or supercriticalhydrocarbon-water (10%)
370°C, 1 hNH
O
1; >90%Kouji Kaiso, Tsunemi Sugimoto, KohichiKashiwagi, and Akio Kamimura*doi:10.1246/cl.2011.370
372 When MicrobubblePolyelectrolyte Com-plexes Overcharge: A Comparative StudyUsing Electrophoresis
Schematic illustrations of charge-neutralized states due to the complexation of cationic polymers and hydroxy ions attached on a microbubble surface are depicted.
Hiroshi Frusawa* and Masaichi Inouedoi:10.1246/cl.2011.372Electronic Supporting Information
375 Nickel-catalyzed Cycloadditions of Benzox-azinones with Alkynes: Synthesis of Quino-lines and Quinolones
N
O
O
R
+ R1 R2
– CO2
1,3-acyl migration
N
N
O
O R
R1
R2
R1
R2
R
Ni(0)/PCyp3
Ni(0)/PBu3
R = Alkoxy
R = Amino
A nickel-catalyzed cycloaddition has been developed where readily available benzoxazinones react with alkynes to afford substituted quinolines or quinolones. The specific cycloaddition can be achieved by tuning substituent R in favor of the formation of quinolines or quinolones selectively.
Nobuyoshi Maizuru, Tasuku Inami, TakuyaKurahashi,* and Seijiro Matsubara*doi:10.1246/cl.2011.375Electronic Supporting Information
378 A Systematic Analysis of Aromatic Hetero-cyclic Rings in Solvatochromic Fluorophores
Sang-Hyun Son, Yuko Abe, Maiko Yuasa,Yutaka Yamagishi, Naoki Sakai, TokiyoshiAyabe, and Koji Yamada*doi:10.1246/cl.2011.378Electronic Supporting Information
381 High-yield Production of cis,cis-MuconicAcid from Catechol in Aqueous Solution byBiocatalyst
OH
OHCatechol
1,2-dioxygenase cis,cis -Muconic acid
(ccMA)
Catechol
(CA)
+ O2
COOH
COOH
High-yield and short-time production of ccMA by a biocatalyst: 415 mM (59.0 g L-1) in 12 h, 100% (mol mol-1) conversion yield.
Aya Kaneko, Yoshitaka Ishii, and KohtaroKirimura*doi:10.1246/cl.2011.381Electronic Supporting Information
Chemistry Letters Vol.40, No.4 (2011)C-36
http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan
384 Enantioselective Pervaporation throughMembranes from Poly(1,3-phenyleneethyn-ylene)-based One-handed Helical Foldamerand Unfoldamer
PMtMt
PMtODo
R
O O
OC12H25
OO
casted from CHCl3 soln.
casted from toluene soln.
n
R =
=
One-handed helical foldamer membrane
Unfoldamer membrane
Enantioselective permeabilities of the membrane consisting of one-handed helical foldamer and unfoldamer were clarified.
Makoto Inoue, Masahiro Teraguchi,* ToshikiAoki, Takeshi Namikoshi, Edy Marwanta, andTakashi Kanekodoi:10.1246/cl.2011.384Electronic Supporting Information
387 Improved Adsorption of Basic Protein onHydroxyapatite Nanoparticles SynthesizedUsing a Lamellar Template of SodiumDodecylphosphate
HOOCHAp
HAp HAp
HAp
HAp LSZ
PO42-
PO42-
OH
+H3N
HOOC
+H3N
LSZ adsorptioncalcination
:phosphate ion
Lamellar template method HAp nanoparticles synthesized using the lamellar template methodshowed an improved adsorption property for basic proteins.
Keizo Nakagawa,* Yosuke Umezaki, KaoriKitamura, Ken-Ichiro Sotowa, and ShigeruSugiyamadoi:10.1246/cl.2011.387
390 Synthesis and Optical Properties of Co-doped ZnO Nanoparticles
350
x = 0.04
x = 0.02
x = 0.01
x = 0
Inte
nsi
ty (
arb
un
it)
λ /nm400 450 500 550 600 650
Luping Zhu,* Yang Yang, and Naici Bingdoi:10.1246/cl.2011.390
393 Switching Reaction Pathways of Benzo[b]-thiophen-3-yllithium and Benzo[b]furan-3-yllithium Based on High-resolution Resi-dence-time and Temperature Control in aFlow Microreactor
Tatsuro Asai, Atsushi Takata, Yousuke Ushiogi,Yoshiharu Iinuma, Aiichiro Nagaki, andJun-ichi Yoshida*doi:10.1246/cl.2011.393Electronic Supporting Information
396 Efficient Dehydration of Aldoximes to Ni-triles Catalyzed by a Lewis Acid Ionic Liquid
SO3Cl-+
(CH2)4
NNMe
SO2Cl
R
N OH
RN
H
Acidic IL
Acetonitrile
R: aryl, alkyl
Acidic IL:
Mizuki Nakajima, Kun Qiao,* NobuhisaKobayashi, Quanxi Bao, Daisuke Tomida, andChiaki Yokoyamadoi:10.1246/cl.2011.396Electronic Supporting Information
Chemistry Letters Vol.40, No.4 (2011) C-37
http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan
398 Nickel-catalyzed Dehydrobrominative Poly-condensation for the Practical Preparation ofRegioregular Poly(3-substituted thiophene)s
S Br
Hex
TMPMgCl.LiCl
THF, rt
Ni cat
rt S
Hex
nH
~>99% H-T regioregularity
N :TMP
Shunsuke Tamba, Shota Tanaka, YouheiOkubo, Hikaru Meguro, Shuji Okamoto, andAtsunori Mori*doi:10.1246/cl.2011.398Electronic Supporting Information
400 Rod-shaped Hydroxyapatite NanoparticleFormation Using AOT and Water withoutOil 200nm
Without AOT
200nm
With AOT
200nm200nm
Without AOT
200nm200nm
With AOT
Hydroxyapatite (HAp) nanoparticles formed with and without AOT
Jun Oshitani,* Nobuhide Kataoka, MikioYoshida, Kuniaki Gotoh, Koreyoshi Imamura,and Hidekazu Tanakadoi:10.1246/cl.2011.400
402 Study of Platinum Dissolution MechanismUsing a Highly Sensitive ElectrochemicalQuartz Crystal Microbalance
Takara Sakurai, Masayo Shibata, ReikoHoriuchi, Ichizo Yagi, and Toshihiro Kondo*doi:10.1246/cl.2011.402
405 Highly Efficient Pd/SiO2Dimethyl SulfoxideCatalyst System for Selective Semihydrog-enation of Alkynes
SiOSiO22
R1 R2 H2+ R2
H
R1
HDMSO
R2
H
R1
H
>95% alkeneselectivityYusuke Takahashi, Norifumi Hashimoto,
Takayoshi Hara, Shogo Shimazu, TakatoMitsudome, Tomoo Mizugaki, KoichiroJitsukawa, and Kiyotomi Kaneda*doi:10.1246/cl.2011.405Electronic Supporting Information
408 In Vitro Cytotoxicity and Intracellular Bio-imaging of Dendritic Platinum Nanoparticlesby Differential Interference Contrast (DIC)
A successful observation of dentritic Pt NPs within live cells using differential interference contrast (DIC) microscopy without labelling fluorescent dyes has been achieved.
Chen-Yu Hong, Yusuke Yamauchi,* andKevin C.-W. Wu*doi:10.1246/cl.2011.408Electronic Supporting Information
Chemistry Letters Vol.40, No.4 (2011)C-38
http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan
410 Synthesis and Characterization of Semicon-ducting Boron-doped Amorphous CarbonMaterials Using an Organic Boron Com-pound as a Precursor
Yasunori Inoue, Masaaki Kitano, KiyotakaNakajima, and Michikazu Hara*doi:10.1246/cl.2011.410
412 Hole Transport of a Liquid-crystalline Phen-ylterthiophene Derivative Exhibiting theNematic Phase at Ambient Temperature
Midori Nuita, Junji Sakuda, Yuki Hirai,Masahiro Funahashi,* and Takashi Kato*doi:10.1246/cl.2011.412Electronic Supporting Information
414 Microwave Synthesis and ElectrochemicalProperties of Ultrafine SnO2 Nanoparticles
Microwave Synthesis of Ultrafine SnO2 NanoparticlesMicrowave Synthesis of Ultrafine SnO2 Nanoparticles
Masashi Yoshinaga,* Norihito Kijima, SonokoWakahara, and Junji Akimotodoi:10.1246/cl.2011.414
417 Synthesis and Characterization of Thie-no[3,4-b]pyrazine Materials for Solution-processible Organic Red Light-emitting Di-odes
OLED
S
N N
300
Stokes shift 300 nm
ELPLUV
Wavelength/nm700600500400
Novel thieno[3,4-b]pyrazine-cored molecules with extra large Stokes shifts of over 300 nm are synthesized and used to fabricate nondoped red-emitting devices by solution-processible technique.Qing Li, Jiuyan Li, Lijun Deng, Qian Wang,
Zhanxian Gao, and Di Liu*doi:10.1246/cl.2011.417Electronic Supporting Information
420 Improved Inactivation Effect of Bacteria:Fabrication of Mesoporous Anatase Filmswith Fine Ag Nanoparticles Prepared byCoaxial Vacuum Arc Deposition
Hamid Oveisi, Simin Rahighi, Xiangfen Jiang,Yoshiaki Agawa, Ali Beitollahi, SoichiWakatsuki, and Yusuke Yamauchi*doi:10.1246/cl.2011.420Electronic Supporting Information
Chemistry Letters Vol.40, No.4 (2011) C-39
http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan
423 [9]Cycloparaphenylene: Nickel-mediatedSynthesis and Crystal Structure
cyclic trimer
THFreflux
[Ni(cod) ]2bpy
MOMO
OMOM
OMOM
OMOM
MOMO
MOMO
MOMO
MOMO
X
X
m -xylene/DMSOreflux
(under air)[9]CPP
NaHSO4·H2O
X = I, Br
Yasutomo Segawa, Petr Šenel, Sanae Matsuura,Haruka Omachi, and Kenichiro Itami*doi:10.1246/cl.2011.423Electronic Supporting Information
Chemistry Letters Vol.40, No.4 (2011)C-40
http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan
