Preparative and mechanistic studies on copper-mediated 1,6-addition reactions to a 2,4-dienone

被引：29

作者：

Uerdingen, M ^{[1
]}

Krause, N ^{[1
]}

机构：

[1] Univ Dortmund, D-44221 Dortmund, Germany

来源：

TETRAHEDRON | 2000年 / 56卷 / 18期

关键词：

copper compounds; dienones; mechanisms; Michael reactions;

D O I：

10.1016/S0040-4020(00)00134-4

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The 2,4-dienone 4a-methyl-4,4a,5,6-tetrahydro-3H-naphthalen-2-one (1) was found to react with cyano-Gilman reagents R2CuLi . LiCN (R=Me, n-Bu, Ph) or Grignard reagents in the presence of catalytic amounts of copper 2-(dimethylaminomethyl)thiophenolate with complete 1,6-regioselectivity and high trans-diastereoselectivity. NMR-spectroscopic investigations revealed that these Michael-additions proceed via pi-complexes 5 which may be transformed into the 1,6-adducts 6 via short-lived copper(III) species. (C) 2000 Elsevier Science Ltd. All rights reserved.

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页码：2799 / 2804

页数：6

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