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