在相转移条件下，α-取代-α-氰基乙酸酯的有机催化对映选择性亲核乙烯基取代反应

Organocatalytic enantioselective nucleophilic vinylic substitution by alpha-substituted-alpha-cyanoacetates under phase-transfer conditions.

作者信息

Bell Mark, Poulsen Thomas B, Jørgensen Karl Anker

机构信息

Danish National Research Foundation: Center for Catalysis, Department of Chemistry, Aarhus University, DK-8000 Aarhus C, Denmark.

出版信息

J Org Chem. 2007 Apr 13;72(8):3053-6. doi: 10.1021/jo070024p. Epub 2007 Mar 20.

DOI:10.1021/jo070024p

PMID:17371076

Abstract

The organocatalytic enantioselective formation of vinyl-substituted all-carbon quaternary stereocenters via nucleophilic vinylic substitution by alpha-substituted-alpha-cyanoacetates is presented. The reaction proceeds well for different alpha-substituted-alpha-cyanoacetates and beta-chloroalkenones using a dimeric cinchona alkaloid phase-transfer catalyst giving the products in good yield and with enantioselectivities up to 98% ee.

摘要

本文介绍了通过α-取代-α-氰基乙酸酯的亲核乙烯基取代反应，实现有机催化对映选择性地形成乙烯基取代的全碳季碳立体中心。使用二聚金鸡纳生物碱相转移催化剂，不同的α-取代-α-氰基乙酸酯和β-氯代烯酮的反应进行良好，产物收率高，对映选择性高达98%ee。