A chemoselective reduction of alkynes to (E)-alkenes

被引：187

作者：

Trost, BM ^{[1
]}

Ball, ZT ^{[1
]}

Jöge, T ^{[1
]}

机构：

[1] Stanford Univ, Dept Chem, Stanford, CA 94305 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2002年 / 124卷 / 27期

关键词：

D O I：

10.1021/ja026457l

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The trans reduction of all types of alkynes to give (E)-olefins is achieved through a two-stage trans hydrosilylation and protodesilylation. Reaction of an alkyne and a silane with the ruthenium catalyst [Cp*Ru(MeCN)3]PF6 results in clean hydrosilylation to give only the (Z)-trans addition product at ambient temperature with catalyst loadings of 1-5 mol %. The crude vinylsilane products are then protodesilylated by the action of cuprous iodide and TBAF at rt-35 °C. The reaction is compatible with many sensitive functional groups and provides a general trans-alkyne reduction not possible by other means. Copyright © 2002 American Chemical Society.

引用

收藏

页码：7922 / 7923

页数：2

相关论文

共 19 条

[1] Strategies for protodesilylation of C-2 trialkylsilyl terminal alkenes [J].

Anderson, JC ;

Flaherty, A .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 2000, (18) :3025-3027

[2] Lewis acid-catalyzed trans-hydrosilylation of alkynes [J].

Asao, N ;

Sudo, T ;

Yamamoto, Y .

JOURNAL OF ORGANIC CHEMISTRY, 1996, 61 (22) :7654-7655

[3] TRIMETHYLSILYLCYCLOOCTADIENE-TRANSITION METAL-COMPLEXES - METAL-CATALYZED PROTODESILYLATION OF CYCLIC VINYLSILANES, AND TRANSFER HYDROGENATION PROMOTED BY THE DISPLACED SILYL GROUP [J].

BANDODAKAR, BS ;

NAGENDRAPPA, G .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 1992, 430 (03) :373-383

[4]

BRANDSMA L, 1999, EUR J ORG CHEM, V775, P5

[5] (+)-ZARAGOZIC-ACID-C - SYNTHESIS AND RELATED STUDIES [J].

CARREIRA, EM ;

DUBOIS, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1995, 117 (31) :8106-8125

[6] REDUCTION OF MULTIPLE BONDS BY LOW-VALENT TRANSITION METAL IONS . HOMOGENEOUS REDUCTION OF ACETYLENES BY CHROMOUS SULFATE [J].

CASTRO, CE ;

STEPHENS, RD .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1964, 86 (20) :4358-&

[7] SYNTHETIC STUDIES ON (2R,4'R,8'R)-ALPHA-TOCOPHEROL FACILE SYNTHESES OF OPTICALLY-ACTIVE, SATURATED, ACYCLIC ISOPRENOIDS VIA STEREOSPECIFIC [3,3] SIGMATROPIC REARRANGEMENTS [J].

CHAN, KK ;

COHEN, N ;

DENOBLE, JP ;

SPECIAN, AC ;

SAUCY, G .

JOURNAL OF ORGANIC CHEMISTRY, 1976, 41 (22) :3497-3505

[8]

CHAN TH, 1979, SYNTHESIS-STUTTGART, P761

[9] Molecular complexes of copper(I):: Easy access to CuF(PPh3)3•2ROH (R = Me or Et) [J].

Chaudhuri, MK ;

Dhar, SS ;

Vijayashree, N .

TRANSITION METAL CHEMISTRY, 2000, 25 (05) :559-561

[10]

HANSON JR, 1974, SYNTHESIS-STUTTGART, P1