Asymmetric Michael addition of malonate anions to prochiral acceptors catalyzed by L-proline rubidium salt

被引:256
作者
Yamaguchi, M
Shiraishi, T
Hirama, M
机构
[1] Department of Chemistry, Graduate School of Science, Tohoku University, Aoba
关键词
D O I
10.1021/jo960216c
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
L-Proline rubidium salt catalyzes the asymmetric Michael addition of malonate anions to prochiral enones and enals. This method can be applied to a wide range of substrates to give adducts with a predictable absolute configuration: (S)-adducts from (E)-enones/enals and (R)-adducts from cyclic (Z)-enones. Both the secondary amine moiety and the carboxylate moiety are critical for the catalytic activity and asymmetric induction. Varying the countercation also affects the reaction course. High enantiomeric excesses were attained when di(tert-butyl) malonate was added to (E)-enones in the presence of CsF. The stereochemistry of the Michael reaction indicates that asymmetric induction takes place via enantioface discrimination involving the acceptor alpha-carbon atom rather than the beta-carbon atom.
引用
收藏
页码:3520 / 3530
页数:11
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