银（I）/硫代ClickFerrophos 配合物催化亚胺叶立德与α-烯酮的高区域选择性和对映选择性 1,3-偶极环加成反应。

Highly endo-selective and enantioselective 1,3-dipolar cycloaddition of azomethine ylide with alpha-enones catalyzed by a silver(I)/ThioClickFerrophos complex.

机构信息

Department of Applied Chemistry, Institute of Science and Engineering, Chuo University, 1-13-27 Kasuga, Bunkyo-ku, Tokyo 112-8551, Japan.

出版信息

Org Lett. 2010 Apr 16;12(8):1752-5. doi: 10.1021/ol100336q.

DOI:10.1021/ol100336q

PMID:20232852

Abstract

A silver(I)/ThioClickFerrophos complex catalyzed the highly endo-selective asymmetric 1,3-dipolar cycloaddition reaction of methyl N-benzylideneglycinate (the source of azomethine ylides) with (E)-acyclic alpha-enones having an endo/exo ratio of 90/10 to 99/1. The highly functionalized endo-4-acyl pyrrolidines were obtained in good yields with high enantioselectivities (up to 98% ee). The complex also effectively catalyzed endo-selective reactions with 2-cyclopentenone to give the endo-bicyclic pyrrolidine in high enantioselectivity.

摘要

银（I）/硫代ClickFerrophos 配合物催化了高度内选择性的不对称 1,3-偶极环加成反应，其中甲基 N-苄基亚氨基甘氨酸酯（亚胺叶立德的来源）与（E）-无环α-烯酮反应，内/外比为 90/10 至 99/1。高功能化的内-4-酰基吡咯烷以高对映选择性（高达 98%ee）获得了良好的产率。该配合物还能有效地催化 2-环戊烯酮的内选择性反应，以高对映选择性得到内双环吡咯烷。