Lewis Acid Promoted Single C-F Bond Activation of the CF3 Group: SN1′-Type 3,3-Difluoroallylation of Arenes with 2-Trifluoromethyl-1-alkenes

被引：159

作者：

Fuchibe, Kohei ^{[1
]}

Hatta, Hibiki ^{[1
]}

Oh, Ken ^{[1
]}

Oki, Rie ^{[1
]}

Ichikawa, Junji ^{[1
]}

机构：

[1] Univ Tsukuba, Div Chem, Fac Pure & Appl Sci, Tsukuba, Ibaraki 3058571, Japan

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 21期

关键词：

allylation; carbocations; C-F bond activation; fluorine; Lewis acids; CONCISE SYNTHESIS; ORGANOLITHIUM REAGENTS; GEM-DIFLUOROALKENES; 3+2 CYCLOADDITION; DIAZO-COMPOUNDS; FLUORINE; CYCLIZATION; HYDRODEFLUORINATION; FUNCTIONALIZATION; TRANSFORMATION;

D O I：

10.1002/anie.201701985

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Activation of the sp(3) C-F bond in 2-trifluoromethyl-1-alkenes was accomplished through treatment with a Lewis acid. In the presence of an equimolar amount of EtAlCl2, the (trifluoromethyl) alkenes readily underwent an S(N)1'-type reaction with arenes through a Friedel-Crafts-type mechanism via elimination of a fluoride ion to afford 3,3-difluoroallylated arenes in good yields. This selective activation of one C-F bond of the CF3 group provides a synthetic method for accessing biologically and synthetically important 1,1-difluoro-1-alkenes.

引用

页码：5890 / 5893

页数：4

共 62 条

[1] Functionalization of Fluorinated Molecules by Transition-Metal-Mediated C-F Bond Activation To Access Fluorinated Building Blocks [J].

Ahrens, Theresia ;

Kohlmann, Johannes ;

Ahrens, Mike ;

Braun, Thomas .

CHEMICAL REVIEWS, 2015, 115 (02) :931-972

[2] C-F Bond Activation in Organic Synthesis [J].

Amii, Hideki ;

Uneyama, Kenji .

CHEMICAL REVIEWS, 2009, 109 (05) :2119-2183

[3]

[Anonymous], 2012, ANGEW CHEM, V124, P12225

[4]

[Anonymous], 2016, ANGEW CHEM, V128, P10562

[5]

[Anonymous], 2008, ANGEW CHEM, V120, P4948

[6]

BEGUE JP, 1995, SYNLETT, P659

[7] 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

[8] A CONCISE SYNTHESIS OF FUNCTIONALIZED GEM-DIFLUOROALKENES VIA THE ADDITION OF ORGANOLITHIUM REAGENTS TO ALPHA-TRIFLUOROMETHYLSTYRENE [J].

BEGUE, JP ;

BONNETDELPON, D ;

ROCK, MH .

TETRAHEDRON LETTERS, 1995, 36 (28) :5003-5006

[9] Use of fluorinated functionality in enzyme inhibitor development: Mechanistic and analytical advantages [J].

Berkowitz, David B. ;

Karukurichi, Kannan R. ;

de la Salud-Bea, Roberto ;

Nelson, David L. ;

McCune, Christopher D. .

JOURNAL OF FLUORINE CHEMISTRY, 2008, 129 (09) :731-742

[10]

Bgu J.-P., 2008, Bioorganic and Medicinal Chemistry of Fluorine

← 1 2 3 4 5 6 7 →