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

被引:74
作者
Evans, PA [1 ]
Leahy, DK [1 ]
机构
[1] Indiana Univ, Dept Chem, Bloomington, IN 47405 USA
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
收藏
页码:8974 / 8975
页数:2
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