Iridium-Catalyzed Enantioselective Allylic Substitution of Unstabilized Enolates Derived from α,β-Unsaturated Ketone

被引：54
作者：
Chen, Ming [1 ]
Hartwig, John F. [1 ]
机构：
[1] Univ Calif Berkeley, Dept Chem, Berkeley, CA 94720 USA
来源：
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2014年 / 53卷 / 33期
基金：
美国国家卫生研究院;
关键词：
asymmetric catalysis; asymmetric allylic substitution; unstabilized enolates; alpha; beta-unsaturated ketones; CYCLOPENTENONE PROSTAGLANDIN ANALOGS; ALPHA-ALKYLATION; ALLYLATION; DIASTEREOSELECTIVITY; AMINATION; CHEMISTRY; MACROLIDE; DIASTEREO; TERTIARY; ENANTIO;
D O I：
10.1002/anie.201403844
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
We report Ir-catalyzed, enantioselective allylic substitution reactions of unstabilized silyl enolates derived from alpha,beta-unsaturated ketones. Asymmetric allylic substitution of a variety of allylic carbonates with silyl enolates gave allylated products in 62-94% yield with 90-98% ee and >20:1 branched-to-linear selectivity. The synthetic utility of this method was illustrated by the short synthesis of an anticancer agent, TEI-9826.
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收藏
页码：8691 / 8695
页数：5
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