Regioselective and enantiospecific rhodium-catalyzed allylic alkylation reactions using copper(I) enolates: Synthesis of (-)-sugiresinol dimethyl ether

被引：75

作者：

Evans, PA ^{[1
]}

Leahy, DK ^{[1
]}

机构：

[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2003年 / 125卷 / 30期

关键词：

D O I：

10.1021/ja035983p

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The transition metal-catalyzed allylic alkylation represents a fundamentally important cross-coupling reaction for the construction of ternary carbon stereogenic centers. We have developed a regioselective and enantiospecific rhodium-catalyzed allylic alkylation of acyclic unsymmetrical allylic alcohol derivatives using copper(I) enolates to prepare β-substituted ketones. This protocol represents a convenient asymmetric Claisen rearrangement surrogate in which α-substituted enolates permit the introduction of an additional stereogenic center. The synthetic utility of this transformation was highlighted in the construction of a trans-1,2-disubstituted cyclohexene and the total synthesis of (-)-sugiresinol dimethyl ether. Finally, we anticipate that copper(I) enolates may prove useful nucleophiles in related metal-catalyzed reactions. Copyright © 2003 American Chemical Society.

引用

页码：8974 / 8975

页数：2

共 26 条

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