Synthesis of gem-Difluoroalkenes via β-Fluoride Elimination of Organorhodium(I)

被引：107

作者：

Miura, Tomoya ^{[1
]}

Ito, Yoshiteru ^{[1
]}

Murakami, Masahiro ^{[1
]}

机构：

[1] Kyoto Univ, Dept Synthet Chem & Biol Chem, Kyoto 6158510, Japan

来源：

CHEMISTRY LETTERS | 2008年 / 37卷 / 09期

关键词：

D O I：

10.1246/cl.2008.1006

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Treatment of alpha-(trifluoromethyl)styrenes with arylboronic esters and MeMgCl in the presence of a rhodium(I) catalyst affords gem-difluoroalkenes. The reaction proceeds through the addition of arylrhodium(I) species across the electron-deficient carbon-carbon double bond and the subsequent beta-floride elimination.

引用

收藏

页码：1006 / 1007

页数：2

相关论文

共 25 条

[1] Addition of organolithium reagents to alpha-(trifluoromethyl)styrene: Concise synthesis of functionalised gem-difluoroalkenes [J].

Begue, JP ;

BonnetDelpon, D ;

Rock, MH .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1996, (12) :1409-1413

[2] Asymmetric nitroallylation of arylboronic acids with nitroallyl acetates catalyzed by chiral rhodium complexes and its application in a concise total synthesis of optically pure (+)-γ-lycorane [J].

Dong, L ;

Xu, YJ ;

Cun, LF ;

Cui, X ;

Mi, AQ ;

Jiang, YZ ;

Gong, LZ .

ORGANIC LETTERS, 2005, 7 (19) :4285-4288

[3] Rhodium-catalyzed carbon-carbon bond forming reactions of organometallic compounds [J].

Fagnou, K ;

Lautens, M .

CHEMICAL REVIEWS, 2003, 103 (01) :169-196

[4]

Fontanelli R., 1965, ANN CHIM-ROME, V55, P862

[5] Catalytic cycle of rhodium-catalyzed asymmetric 1,4-addition of organoboronic acids.: Arylrhodium, oxa-π-allylrhodium, and hydroxorhodium intermediates [J].

Hayashi, T ;

Takahashi, M ;

Takaya, Y ;

Ogasawara, M .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (18) :5052-5058

[6] Rhodium-catalyzed asymmetric 1,4-addition and its related asymmetric reactions [J].

Hayashi, T ;

Yamasaki, K .

CHEMICAL REVIEWS, 2003, 103 (08) :2829-2844

[7]

HEITZ W, 1991, MAKROMOL CHEM-RAPID, V12, P69

[8] 1-Trifluoromethylvinylsilane as a CF2=C--CH2+ synthon:: Synthesis of functionalized 1,1-difluoro-1-alkenes via isolable 2,2-difluorovinylsilanes [J].

Ichikawa, J ;

Fukui, H ;

Ishibashi, Y .

JOURNAL OF ORGANIC CHEMISTRY, 2003, 68 (20) :7800-7805

[9] gem-difluoroolefin synthesis:: general methods via thermostable difluorovinylmetals starting from 2,2,2-trifluoroethanol derivatives [J].

Ichikawa, J .

JOURNAL OF FLUORINE CHEMISTRY, 2000, 105 (02) :257-263

[10] 5-endo Heck-type cyclization of 2-(trifluoromethyl)allyl ketone oximes:: synthesis of 4-difluoromethylene-substituted 1-pyrrolines [J].

Ichikawa, Junji ;

Nadano, Ryo ;

Ito, Naotaka .

CHEMICAL COMMUNICATIONS, 2006, (42) :4425-4427