双核镍催化下，α,β-不饱和γ-丁内酰胺的直接不对称乙烯基曼尼希型和迈克尔反应。

Direct catalytic asymmetric vinylogous Mannich-type and Michael reactions of an alpha,beta-unsaturated gamma-butyrolactam under dinuclear nickel catalysis.

机构信息

Graduate School of Pharmaceutical Sciences, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.

出版信息

J Am Chem Soc. 2010 Mar 24;132(11):3666-7. doi: 10.1021/ja1002636.

PMID:20192184

Abstract

Direct catalytic asymmetric vinylogous reactions of an alpha,beta-unsaturated gamma-butyrolactam as a donor are described. A homodinuclear Ni(2)-Schiff base complex promoted a vinylogous Mannich-type reaction of N-Boc imines as well as a vinylogous Michael reaction to nitroalkenes selectively at the gamma-position under simple proton-transfer conditions. Vinylogous Mannich adducts were obtained in 5:1-->30:1 dr and 99% ee, and vinylogous Michael adducts were obtained in 16:1-->30:1 dr and 93-99% ee.

摘要

描述了一种作为供体的α，β-不饱和γ-丁内酯的直接催化不对称烯醇式反应。双核 Ni(2)-席夫碱配合物在简单的质子转移条件下，选择性地在γ-位促进 N-Boc 亚胺的烯醇式 Mannich 型反应以及与硝基烯烃的烯醇式 Michael 反应。烯醇式 Mannich 加合物以 5:1-->30:1 dr 和 99%ee 获得，而烯醇式 Michael 加合物以 16:1-->30:1 dr 和 93-99%ee 获得。