Chemistry Lettershttp://www.csj.jp/journals/chem-lett/

Vol.40 No.9 CMLTAGSeptember, 2011 ISSN 0366-7022

Copyright © 2011 The Chemical Society of Japan

Highlight Review

894 Cross-coupling Reactions of Organoboranes:An Easy Method for C­C Bonding

B R B B RC B

X R X X RCR-X

R-B

C-X

C-

Akira Suzuki and Yasunori Yamamotodoi:10.1246/cl.2011.894

The Csp2­B compounds and Csp3­B compounds readily cross-couple with organic electrophiles to give coupled productsselectively in high yields. Recently, the Csp­B compounds have been also observed to react with organic electrophiles to produceexpected cross-coupled products. The overview of some of such coupling reactions is discussed here in this article.

Letter

902 A Hexameric Porphyrin Triangle Con-structed by Suzuki­Miyaura Cross-couplingReaction

Jianxin Song, Shoma Anabuki, Naoki Aratani,*Hiroshi Shinokubo,* and Atsuhiro Osuka*doi:10.1246/cl.2011.902Electronic Supporting Information

904 Bis(cyclopentadienyldicarbonyliron) as aConvenient Carbon Monoxide Source inPalladium-catalyzed Carbonylative Cou-pling of Aryl Iodides with Amines, Alcohols,and Thiols

Ryotaro Nakaya, Hideki Yorimitsu,* andKoichiro Oshima*doi:10.1246/cl.2011.904Electronic Supporting Information

907 Phosphane-free Suzuki­Miyaura Couplingof Aryl Imidazolesulfonates with Arylbo-ronic Acids and Potassium Aryltrifluorobo-rates under Aqueous Conditions

O

O

O

NNAr

+ Ar'BX

BX = B(OH)2, BF3K

1 (1 mol% Pd), KOH, TBAB

MeOH/H2O: 3/1, 110 °C, 1dAr Ar'

53-99%

1a, R1 = Me, R2 = OH1b, R1 = 4-ClC6H4, R2 = Cl

PdN

R1

OH

Cl )2R2

Aryl imidazole-1-sulfonates are efficiently cross-coupled with arylboronic acids and potassium aryltrifluoroborates using only 0.5 mol % of oxime palladacycles 1 under aqueous conditions at 110 °C. Under these simple phosphane-free reaction conditions a wide array of biaryl derivatives has been prepared in high yields. This methodology allows the using of microwave irradiation conditions.

S

José Francisco Cívicos, MohammadGholinejad, Diego A. Alonso,* and CarmenNájera*doi:10.1246/cl.2011.907Electronic Supporting Information

910 Pd/C-catalyzed andWater-mediated HiyamaCross-coupling Reaction Using an Electron-deficient Phosphine Ligand

R1

X Si(OEt)3R2 R1 R2

10% Pd/C (0.5 mol%)(4-FC6H4)3P (1.0 mol%)TBAF·3H2O (2 equiv)

4.8% aq. toluene, reflux

1.5 equiv1 mmol

X = Cl, Br, ITakayoshi Yanase, Shigeki Mori, YasunariMonguchi, and Hironao Sajiki*doi:10.1246/cl.2011.910Electronic Supporting Information

913 An Improvement of Nickel Catalyst forCross-coupling Reaction of ArylboronicAcids with Aryl Carbonates by Using aFerrocenyl Bisphosphine Ligand OCOMe B

O

+R1 R2 cat. [Ni] – Ligand

K2CO3, Toluene

R1 R2

Ligand = PCy3

Ligand = DCyPF

Low Yield (<3%)

46–95%Fe

PCy2

PCy2 DCyPFRyoichi Kuwano* and Ryosuke Shimizudoi:10.1246/cl.2011.913Electronic Supporting Information

916 Ruthenium-catalyzed C­H Silylation ofMethylboronic Acid Using a Removable¡-Directing Modifier on the Boron Atom

HN N NBC

HH

H

MeB(pza)

Ru cat.PhMe2SiHnorbornene

toluene135 °C

HN N NBC

PhMe2SiH

H

thenpinacolTsOH

PhMe2SiCH2B(pza)

CPhMe2Si

HH

OB

O

PhMe2SiCH2B(pin)

Attachment of a 2-(1H-pyrazol-3-yl)aniline-derived modifier on the boron atom of methylboronic acid enables Ru-catalyzed C–H silylation at the α-carbon atom, to which the boron atom is bound.

α

Hideki Ihara, Akinori Ueda, and MichinoriSuginome*doi:10.1246/cl.2011.916Electronic Supporting Information

Chemistry Letters Vol.40, No.9 (2011)C-86

http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan

919 Divergent Synthesis of 2,5-DiarylphospholesBased on Cross-coupling Reactions: Sub-stituent Effects on the Optical and RedoxProperties of Benzene­Phosphole­Benzene³-Systems

PEPh XX

SnBu3PO

Bu3Sn

Ph

IPO

I

Ph

Stille Stille, Negishi

Yoshihiro Matano,* Yusuke Kon, Arihiro Saito,Yoshifumi Kimura, Toshihiro Murafuji, andHiroshi Imahoridoi:10.1246/cl.2011.919Electronic Supporting Information

922 Synthesis and Properties of Seleno-analogMK-organic Dye for Photovoltaic CellsPrepared by C­H Functionalization Reac-tions of Selenophene Derivatives

Shunsuke Tamba, Ryosuke Fujii, AtsunoriMori,* Kohjiro Hara, and Nagatoshi Koumura*doi:10.1246/cl.2011.922Electronic Supporting Information

925 Copper-free Sonogashira Coupling ReactionUsing a trans-Spanning 1,2-Bis(2-thienyl-ethynyl)benzene Ligand

Shingo Atobe, Motohiro Sonoda,* Yuki Suzuki,Hiroyuki Shinohara, Takuya Yamamoto, andAkiya Ogawa*doi:10.1246/cl.2011.925Electronic Supporting Information

928 Copper-catalyzed Conjugate Additions ofAlkylboranes to Aryl ¡,¢-UnsaturatedKetones

Hirohisa Ohmiya,* Yoshinori Shido, MikaYoshida, and Masaya Sawamura*doi:10.1246/cl.2011.928

931 Facile Preparation of Macrocycles withTriphenylamine Backbone via C­N CouplingReaction

NN

N N

N

n

n = 1 ~ 3

n -Bu

n -Bun -Bu

n -Bu n -BuCTPA

HNBr

Pd(OAc)2P(t-Bu)3t-BuONa

toluenereflux, 24 h

n -Bu

Kousuke Tsuchiya,* Hiroko Miyaishi, andKenji Oginodoi:10.1246/cl.2011.931Electronic Supporting Information

Chemistry Letters Vol.40, No.9 (2011) C-87

http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan

934 C­N and C­S Bond Forming Cross Couplingin Water with Amphiphilic Resin-supportedPalladium Complexes

Yoshinori Hirai and Yasuhiro Uozumi*doi:10.1246/cl.2011.934

936 Kumada­Tamao­Corriu Coupling Using N-Heterocyclic Carbene Ligands Bearing Pyr-idyl and Ethylenedioxyl Moieties

Ar1 X Ar1 Ar2

N NO

O

Br

N 1aTHF

Ni(acac)2]•H[ 2O (1 mol %)1a (1.2 mol %)

Ar2MgBr (2.5 equiv)

Koichi Mitsudo,* Yuta Doi, SyunsukeSakamoto, Hiroki Murakami, Hiroki Mandai,and Seiji Suga*doi:10.1246/cl.2011.936Electronic Supporting Information

939 Direct Sequential C3 and C1 ArylationReaction of Imidazo[1,5-a]pyridine Cata-lyzed by a 1,10-Phenanthroline­PalladiumComplex

NN

I IOMe CF3

MeO

CF3

(1.1 equiv)Cs2CO3 (3 equiv)

(2 equiv)

DMA, 150 °C, 20 h 150 °C, 20 h

61%

N

N

N

NPd

2+

2PF6-

[Pd(phen)2](PF6)2(10 mol%)

NN

H

H

[Pd(phen)2](PF6)2Sequential diarylation in one-pot

Eiji Yamaguchi, Fumitoshi Shibahara,* andToshiaki Murai*doi:10.1246/cl.2011.939Electronic Supporting Information

941 2,7-Diborylanthracene as a Useful BuildingBlock for Extended ³-Conjugated Aromatics

Ryota Ozawa, Kenji Yoza, and KenjiKobayashi*doi:10.1246/cl.2011.941Electronic Supporting Information

944 Synthesis and Multistimuli-responsive Be-havior of Octaethylporphyrin­Dihexylbithio-phene­Dimethylaniline Triads Connectedwith Diacetylene Linkages

Junro Yoshino,* Mizuki Tsujiguchi, NaotoHayashi, and Hiroyuki Higuchi*doi:10.1246/cl.2011.944Electronic Supporting Information

Chemistry Letters Vol.40, No.9 (2011)C-88

http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan

947 Exchange of Quinone and HydroquinoneMoieties in Mixed Solutions of Biquinoneand Bihydroquinone

O

O O

O

O

OO

O

H

H

HH

O

OO

O

O

O O

O

H

H

HH

O

O O

O

O

OO

OH

H

H

H

(HQ1)2 (QQ1)(HH1)

e

e

H

H

HHNaoto Hayashi,* Kiyomi Matsui, Akifumi

Kanda, Takahiro Yoshikawa, HiroyukiNakagawa, Junro Yoshino, and HiroyukiHiguchi*doi:10.1246/cl.2011.947Electronic Supporting Information

950 Suzuki­Miyaura Cross Coupling Reactionsof B-Allenyl-9-BBN

B

I

COOEt

NaOMe, [Pd(PPh3)4] cat.

DMF, RT

COOEt

70%Karin Radkowski, Günter Seidel, and AloisFürstner*doi:10.1246/cl.2011.950

953 Palladium-catalyzed Regio- and Diastereo-selective Allylic Alkylation in Ionic Liquids

Me Ph

OAc

MeCO2Et

O

Me

+Me

PhCO2Et

Me

O

Me

5 mol% Pd(OAc)210 mol% 2-DPPBA

NaHMDSIL (solvent)

60 °C, 12 h, 80%

EtNEtMe

OMe

–NTf2

+

>98% regioselectivity83% diastereoselectivity

Pd in IL: 9 times of reuse=IL Motoi Kawatsura,* Hideyuki Nobuto,Shunsuke Hayashi, Takuya Hirakawa, DaijiIkeda, and Toshiyuki Itoh*doi:10.1246/cl.2011.953

956 Ligand-free Fe­Cu Cocatalyzed Cross-cou-pling of Terminal Alkynes with Aryl Halides

R + I CuFe2O4 (10 mol%)

Cs2CO3, N2, 24hR

R' R'

Copper ferrite-nanoparticle-mediated cross-coupling of terminal alkynes with aryl halides under ligand-free conditions was demonstrated. The magnetic nature of the copper ferrite nanoparticles was exploited for easy and quantitative separation of the catalyst. Leaching of Fe and Cu to the reaction medium was found to be within permissible limit and the activity of the catalyst was almost unaltered up to three consecutive cycles.

Niranjan Panda,* Ashis Kumar Jena, andSasmita Mohapatradoi:10.1246/cl.2011.956

959 Synthesis of Acylsilanes by Palladium-cata-lyzed Cross-coupling Reaction of ThiolEsters and Silylzinc Chlorides

R

O

SPh

PhMe2Si–ZnClcat. [Pd(dba) ]2cat. (c -Hex)3P

THF-Et2Ort

R

O

SiMe2Ph

An acylsilane synthesis by a Pd-catalyzed cross-coupling reaction of thiol esters and silylzinc chlorides was developed. (S )-Phenyl thiol esters with a variety of functional groups were converted to corresponding acylsilanes.

Hiroki Azuma, Kentaro Okano, and HidetoshiTokuyama*doi:10.1246/cl.2011.959Electronic Supporting Information

Chemistry Letters Vol.40, No.9 (2011) C-89

http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan

962 Palladium-catalyzed Borylation of ArylArenesulfonates with Dialkoxyboranes

100 °C

ArSO3

FG

HBO

OMeMe

Me

Me

+ B

FG

O

O

MeMe

Me

Me

[Pd(dba)2] / D-t -BPFEt3N

Bu4NI

dioxane

Ar = 4-MeC6H5, Ph, 4-CF3C6H5

Miki Murata,* Takeshi Oda, Yosuke Sogabe,Hirofumi Tone, Takeshi Namikoshi, and ShinjiWatanabedoi:10.1246/cl.2011.962Electronic Supporting Information

964 Systematic Synthesis and Characterizationof a Series of Tetra(5-aryl-2-thienyl)thio-phenes

S

S S

S S

Br Br

Br Br

Cs2CO3, [Pd(PPh3) ]4

Ar-B(OH)2

DMF-H2OAr = Ph, p -BuC6H4,

p -MeOC6H4, p -CF3C6H4

S

S S

S S

X

X X

XX = H, Bu, OMe, CF3

We have succeeded in the synthesis of a series of tetra(5-aryl-2-thienyl)thiophenes as the aryl-functionalized tetrathienylthiophenes. The electrochemical properties were examined by cyclic voltammetry. The CV of the all compounds showed that the redox behavior and potentials were controlled by the electronic effect of the p-substituted phenyl groups introduced at the outer

-positions on the four thiophene units linked to the thiophene core. α

Hiroki Muraoka, Takanori Tanifuji, and SatoshiOgawa*doi:10.1246/cl.2011.964Electronic Supporting Information

967 Chemoselective Transfer of Allyl or PhenylGroup from Allyl(phenyl)germanes in Pd-catalyzed Reactions with Aryl Halides

Ar

ArX/Pd/NaOHGe n

4-n

n = 1, 2 or 3Ar

2. ArX/Pd/TBAF

1. SbF5/Ctoluene

dioxane/H2O

Jean-Philippe Pitteloud, Yong Liang, andStanislaw F. Wnuk*doi:10.1246/cl.2011.967Electronic Supporting Information

970 Introduction of Two Anthracene Moietiesinto Perylenebis(dicarboximide) Core bySuzuki­Miyaura Coupling toward Construc-tion of Donor­Acceptor­Donor Arrays

N

N

OO

OO

R

R

Suzuki-MiyauraCoupling

Tetsuo Iwanaga, Hiroko Ida, Makoto Takezaki,and Shinji Toyota*doi:10.1246/cl.2011.970Electronic Supporting Information

972 Copper-catalyzed Sila-Sonogashira­HagiharaCross-coupling Reactions of Alkynylsilaneswith Aryl Iodides under Palladium-freeConditions

DMI, 120 °C

R1 = aromatic, heteroaromatic, aliphaticR2 = aromatic, heteroaromatic

R1 R2

CuCl (5 mol%)

SiMe3 +R1 R2I

PPh3 (5 mol%)

PhCO2K (1.0 equiv)

(1.2 equiv) (1.0 equiv) 44-97%25 examplesYasushi Nishihara,* Shintaro Noyori, Takeru

Okamoto, Masato Suetsugu, and MasayukiIwasakidoi:10.1246/cl.2011.972Electronic Supporting Information

Chemistry Letters Vol.40, No.9 (2011)C-90

http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan

975 1,4-Diaryl-7,10-dimethoxyquinoxalino[2,3-b]-quinoxalines and Their Dihydro Derivatives:Redox Switching of NIR Absorption andFluorescence

Youhei Miura, Hidetoshi Kawai, KenshuFujiwara, and Takanori Suzuki*doi:10.1246/cl.2011.975Electronic Supporting Information

978 Pd-catalyzed Highly Regio- and Stereo-controlled Direct Alkenylation of Electron-deficient Polyfluoroarenes

H

+Pd(PPh3)4 (5 mol%)

Ag2CO3 (0.5 equiv)DMSO, 70 °C

FF

F

FF

IPh

F

FF

F

F

66% yield12 examples, yield up to 87%

Ph

Fei Chen and Xingang Zhang*doi:10.1246/cl.2011.978Electronic Supporting Information

980 Palladium-catalyzed Carbon­Sulfur Cross-coupling Reactions of Aryl Chlorides withIndium Tris(organothiolates) Cl

(RS)3In

DMF, 110 °C

SR

(0.35 equiv)

cat. Pd(OAc)2, Xantphos

Cs2CO3 or DIPEAFG FG+

R = i -Pr, t -Bu, Ph, p -Anisyl, p -Tolyl

FG = NO2, Ac, EtO2C, CHO, CN,

Hetaryl-Cl = 2-chloropyrimidine, 2-chloropyrazineJuntae Mo, Dahan Eom, Sung Hong Kim, andPhil Ho Lee*doi:10.1246/cl.2011.980Electronic Supporting Information

983 Synthesis of Iron(III) Complex BearingTridentate ¢-Aminoketonato Ligand: Appli-cation to Iron-catalyzed Cross-coupling Re-action of Arylmagnesium Bromides withAlkyl Halides

MgBr1 (1.0 mol%)

Et2O, rt, 5min87%

1

Br

+

Yoshitaka Yamaguchi,* Hiroaki Ando, MakotoNagaya, Hideto Hinago, Takashi Ito, andMasatoshi Asami*doi:10.1246/cl.2011.983Electronic Supporting Information

986 Facile Synthesis of ¢,¢-Difluorostyrenes viathe Negishi Coupling of Thermally Stable2,2-Difluorovinyl Zinc­TMEDA Complex

CF2 H

H1. s -BuLi TMEDA

CF2 ZnCl•TMEDA

H cat. Pd(0)H

CF2 R

stable, storable

RX

X = I, Br, Cl, OTf

2. ZnCl2

Takeshi Fujita, Tomohiro Ichitsuka, KoheiFuchibe, and Junji Ichikawa*doi:10.1246/cl.2011.986

Chemistry Letters Vol.40, No.9 (2011) C-91

http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan

989 Spectral Shifts of the Environment-sensitiveFluorophore POLARIC· in HeterogeneousInterfaces

Sang-Hyun Son, Yutaka Yamagishi, MichikoTani, Maiko Yuasa, and Koji Yamada*doi:10.1246/cl.2011.989Electronic Supporting Information

992 Preparation of Head-to-tail ³-ConjugatedPoly(thiophene­pyridine) and Polypyrimi-dine by Organometallic Polycondensation Regioregular Polymer-1, its alkyl derivatives, and Polymer-2 have been synthesized.

S NBrBr

S NBrClMg

1S N

Polymer-1

N

NI

2

BrN

NMgCl

4

Br

3n

N

N

Polymer-2

n

+ i -PrMgClTHF [NiCl2(diphos)]

23

5

6

24

5

24

5

6

11

3

1

3 4

Hiroki Fukumoto, Yoshiki Fujiwara, andTakakazu Yamamoto*doi:10.1246/cl.2011.992Electronic Supporting Information

995 Stereocontrolled Formation of Styrenes byPd(0)-catalyzed Cross-coupling of Photoacti-vated (E)-Alkenylgermanes with Aryl Bro-mides

Pd(0), F

hvCu(BF4)2

R1Ar ArR1

H

H

HH

+R1Ge

XX

C8F17

R1

ArH

H

+

X = CH2(2-Nap)X = F

Ar-Br(3 equiv)

β-(E )67-100%

β-(Z )0-20%

α0-26%

14 examples (40-72% overall yields)

The stereocontrolled synthesis of (E )-configured styrenes via Pd(0)-catalyzed cross-coupingof (E )-alkenylgermanes with aryl bromides is described.

Chih-Chung Tseng, Mungyuen Li, Bingli Mo,Sarah A. Warren, and Alan C. Spivey*doi:10.1246/cl.2011.995Electronic Supporting Information

998 n-Type Field-effect Transistors Based onThieno[3,2-b]thiophene-2,5-dione and theBis(dicyanomethylene) Derivatives

S

S

F3C

CF3O

O

1

S

S

F3C

CF3

2

NC

CN

CN

CNShiyan Chen, Altan Bolag, Jun-ichi Nishida,and Yoshiro Yamashita*doi:10.1246/cl.2011.998Electronic Supporting Information

1001 Cross-coupling of Aryl/Alkenyl Silyl Etherswith Grignard Reagents through Nickel-catalyzed C­O Bond Activation

O ArAr-MSi

Ni catalyst

OMSi

The Ni-Catalyzed Kumada–Tamao–Corriu coupling reaction based on C–O bond cleavage ofsiloxy arenes/alkenes was described in this letter.

Fei Zhao, Da-Gang Yu, Ru-Yi Zhu, ZhenfengXi,* and Zhang-Jie Shi*doi:10.1246/cl.2011.1001Electronic Supporting Information

Chemistry Letters Vol.40, No.9 (2011)C-92

http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan

1004 Pd(II)-catalyzed Cross-coupling of C(sp2)­HBonds and Alkyl­, Aryl­, and Vinyl­BoronReagents via Pd(II)/Pd(0) Catalysis

Masayuki Wasa, Kelvin S. L. Chan, andJin-Quan Yu*doi:10.1246/cl.2011.1004Electronic Supporting Information

1007 Iridium-catalyzed ortho-C­H Borylation ofAryl Ketones with Bis(pinacolato)diboron

BO

OB

O

O

+

1/2[Ir(OMe)(cod)]2-2AsPh3 (3 mol%)

B2pin2 =

B2pin2R

O

FG

R

O

FGBpin

octane/120 °C

Hiroshi Itoh, Takao Kikuchi, Tatsuo Ishiyama,*and Norio Miyaura*doi:10.1246/cl.2011.1007Electronic Supporting Information

1009 Palladium-catalyzed Cross-coupling of ArylIodides with ¢-Trimethylsiloxy-¡-diazoest-ers: A Novel Approach toward ¢-Keto-¡-arylesters

R

OSiMe3

CO2Et

N2

R

O

CO2Et

Ar

+ ArI1) cat. Pd(0)

2) HZhibin Shu, Ji Zhang, Yan Zhang, and JianboWang*doi:10.1246/cl.2011.1009Electronic Supporting Information

1012 Iron-catalyzed Chemoselective Cross-cou-pling of ¡-Bromocarboxylic Acid Derivativeswith Aryl Grignard Reagents

Masayoshi Jin and Masaharu Nakamura*doi:10.1246/cl.2011.1012

1015 Palladium-catalyzed Direct Monoarylationof Thiophene-, Benzothiophene-, and Indole-acetic Acids through Regioselective C­HBond Cleavage S

Y

CO2H

CO2H

H

H

Y = S, NR

S

Y

CO2H

CO2H

Ar

Ar

Pd-cat.

ArBr

Daisuke Takeda, Mana Yamashita, Koji Hirano,Tetsuya Satoh,* and Masahiro Miura*doi:10.1246/cl.2011.1015Electronic Supporting Information

Chemistry Letters Vol.40, No.9 (2011) C-93

http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan

1018 Ruthenium-catalyzed Acylation of Arylpyr-idines with Acyl Chlorides via ortho-SelectiveC­H Bond Cleavage

N N

O

RR' R'

H

R" R"acylation

Cl

O

R+

R = aryl, alkenyl

cat. [RuCl2(PPh3) ]3

K2CO3

Ruthenium-catalyzed ortho-selective acylation of arylpyridines with acyl chlorides via C−H bond cleavage is described. Aromatic acyl chlorides as well as , -unsaturated acyl chlorides were coupled with arylpyridines to give aromatic ketones in the presence of [RuCl2(PPh3)3] as a catalyst and potassium carbonate as a base.

α β

Takuya Kochi, Aoi Tazawa, Kazuki Honda, andFumitoshi Kakiuchi*doi:10.1246/cl.2011.1018Electronic Supporting Information

1021 Synthesis and Properties of Acetylene-bridged N-Confused Porphyrin Dimers

Motoki Toganoh, Takumi Takayama, NandyRitesh, Nobuo Kimizuka, and Hiroyuki Furuta*doi:10.1246/cl.2011.1021Electronic Supporting Information

1024 Kinetic Studies of the Ni-catalyzed Cross-coupling of Alkyl Halides and a Tosylatewith Butyl Grignard Reagent in the Presenceof 1,3-Butadiene

Relative reactivity ofprimary Alkyl–X

Alkyl–OTs:Alkyl–Br:Alkyl–I1:50:1000≈

51.2 ± 2.6

57.3 ± 4.0

52.7 ± 4.9n -Nonyl–Br

n -Hexyl–I

n -Heptyl–OTs

Alkyl–X n -BuMgCl

ΔH /kJ mol–1

THF

ΔS /J K–1mol–1

Alkyl–n -Bu

++++

–14.8 ± 12.3

–16.9 ± 16.7

–67.6 ± 18.0

+

NiBr2·dme1,3-butadiene

X = OTs, Br, I

ΔG273 /kJ mol–1++

55.3 ± 6.0

61.9 ± 8.6

71.1 ± 9.8

Alkyl–X

Takanori Iwasaki, Asako Tsumura, TakehiroOmori, Hitoshi Kuniyasu, Jun Terao, andNobuaki Kambe*doi:10.1246/cl.2011.1024

1027 Copper-free Sonogashira Coupling Reactionin Phosphonium Amino Acid Ionic Liquids

hexane

K2CO3 aq.

n -C10H21PBu3

n -C7H15NH COO

Ph

ionic liquid+

Pd-catalystBr H

Cu- and Amine-Free Sonogashira Coupling

recyclable

Takahide Fukuyama,* Md. Taifur Rahman,Shinji Maetani, and Ilhyong Ryu*doi:10.1246/cl.2011.1027

1030 Kumada­Tamao­Corriu Coupling of AlkylHalides Catalyzed by an Iron­BisphosphineComplex

Alkyl X + Alkyl Ar

cat. [FeCl2(SciOPP)](0.5–3.0 mol%)

THF, 25–40 °Cslow additionX = Cl, Br, I

ArMgBr PP

t-Bu

t-Bu

t-Bu

t-Bu

t-Bu

t-Bu

t-Bu

t-Bu

Fe

Cl Cl

[FeCl2(SciOPP)]

74–98% yield10 examples

Takuji Hatakeyama, Yu-ichi Fujiwara,Yoshihiro Okada, Takuma Itoh, ToruHashimoto, Shintaro Kawamura, Kazuki Ogata,Hikaru Takaya, and Masaharu Nakamura*doi:10.1246/cl.2011.1030Electronic Supporting Information

Chemistry Letters Vol.40, No.9 (2011)C-94

http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan

1033 Triarylamines on [3]Radialene Scaffold:Novel [3]Radialene-based, Multistep, Wide-range Redox Systems with Remarkably LowOxidation Potentials

The title compounds show an amphoteric, multistep redox potentials owing to the electron-donating triarylamine moieties and the electron-accepting [3]radialene core. The intramolecular through-space interaction between the facing triarylamine groups makes their oxidation potentials remarkably lower.

Kouzou Matsumoto,* Nao Yamada, TetsuyaEnomoto, Hiroyuki Kurata, Takeshi Kawase,and Masaji Odadoi:10.1246/cl.2011.1033Electronic Supporting Information

1036 Monovalent Nickel Complex Bearing aBulky N-Heterocyclic Carbene CatalyzesBuchwald­Hartwig Amination of Aryl Hal-ides under Mild Conditions

Ni(I) catalyst

+

Ni(I) (5 mol%)PPh3 (25 mol%)

toluene, NaOt -Bu,r.t. ~ 70°C

Ph2NH Ph2NR

XR

Shinya Nagao, Taisuke Matsumoto, Yuji Koga,and Kouki Matsubara*doi:10.1246/cl.2011.1036Electronic Supporting Information

1039 Synthesis and Properties of Polymer HavingElectronegative Terthiophene PendantsBased on Cyclopenta[c]thiophene

S

OO

SS

n

S

OO

SS

Polymerization

–2.5Potential / V

–1.0–2.0 –1.5 –0.5

+

Cur

rent

/ ar

b un

itYutaka Ie,* Atsuki Yoshimura, DaisukeTakeuchi, Kohtaro Osakada, and Yoshio Aso*doi:10.1246/cl.2011.1039Electronic Supporting Information

1041 Iron-catalyzed Oxidative Coupling of Alkyl-amines with Arenes, Nitroalkanes, and 1,3-Dicarbonyl Compounds

Eiji Shirakawa,* Tomoki Yoneda, KoheiMoriya, Kensuke Ota, Nanase Uchiyama, RyoNishikawa, and Tamio Hayashi*doi:10.1246/cl.2011.1041Electronic Supporting Information

1044 Mechanistic Insight into the Anomalous syn-Selectivity Observed during the Addition ofAllenylboronates to Aromatic Aldehydes

syn-(1S,2R )

C C C

Bu

B(pin)H

Me

98% ee

PhCHOC

CC

Bu

Ph

HMe

H OHBF3·OEt 2

C C C

Bu

BHC

C OH

H

HH

cyclic transition state withCH/π interactions (M06-2X/6-31+G**)

anti /syn = 29:71> 97% ee

(S )

The reaction of enantioenriched allenylboronate (98% enantiomeric excess [ee]) with benzaldehyde gave the corresponding homopropargylic alcohol in an anomalous 1,2-syn-selectivity (anti/syn = 29:71) with high ee (98% and 97%, respectively). The stereochemical outcome, in terms of the absolute configuration, shows that this reaction proceeds through a cyclic transition state. DFT calculations were carried out to elucidate the mechanism of this anomalous syn-selectivity in the reaction of aromatic aldehydes.

Yusuke Sasaki, Masaya Sawamura, and HajimeIto*doi:10.1246/cl.2011.1044Electronic Supporting Information

Chemistry Letters Vol.40, No.9 (2011) C-95

http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan

1047 Synthesis of Phenanthridinones and Phenan-thridine Derivatives through Palladium-cat-alyzed Oxidative C­H Coupling of Benzani-lides

A palladium-catalyzed oxidative C–H coupling reaction of benzanilides using molecular oxygen as the oxidant furnishes phenanthridinones. The palladium-catalyzed reaction in combination with simple derivatization provides an efficient access to a phenanthridine skeleton starting from readily available benzoic acids and anilines.

Naoki Ishida, Yuuta Nakanishi, TaisakuMoriya, and Masahiro Murakami*doi:10.1246/cl.2011.1047Electronic Supporting Information

1050 Palladium-catalyzed Direct C­H Bond Aryl-ation of Simple Arenes with Aryltrimethyl-silanes

+1,2-DCE

80°C

PdCl2 / CuCl2SiMe3H

R

R

C-H, C-Si cross-couplingKenji Funaki, Hiroshi Kawai, Tetsuo Sato, andShuichi Oi*doi:10.1246/cl.2011.1050Electronic Supporting Information

1053 Palladium-catalyzed Highly RegioselectiveC-3 Arylation of Imidazo[1,5-a]pyridine

NN

H

+ ArBrPd/L

Base NN

Ar

A direct palladium-catalyzed highly regioselective C-3 arylation of imidazo[1,5-a]pyridine has been developed. This method is efficient with a variety of aryl bromides, as well as with selected hetaryl bromides.

Chunhui Huang, Alexandros Giokaris, andVladimir Gevorgyan*doi:10.1246/cl.2011.1053Electronic Supporting Information

1055 Iridium-catalyzed ¡-Alkylation of Aceto-nitrile with Primary and Secondary Alcohols

+

cat. [Ir(OH)(cod)]2 / PPh3

1,4-Dioxane, 130 °CCH3CN

R1 OH R1 CN

R2 R2cat. t -BuOK

Takuya Sawaguchi and Yasushi Obora*doi:10.1246/cl.2011.1055Electronic Supporting Information

Chemistry Letters Vol.40, No.9 (2011)C-96

http://www.csj.jp/journals/chem-lett/Copyright © 2011 The Chemical Society of Japan