在低配体负载下，通过直接的有机催化不对称α-异硫氰酸根合亚胺与α-酮酯的Aldol 反应：一种双立体控制方法，用于合成具有手性季碳中心的环状硫代氨基甲酸酯。

Direct organocatalytic asymmetric aldol reaction of alpha-isothiocyanato imides to alpha-ketoesters under low ligand loading: a doubly stereocontrolled approach to cyclic thiocarbamates bearing chiral quaternary stereocenters.

机构信息

State Key Laboratory of Applied Organic Chemistry, Institute of Biochemistry and Molecular Biology, Key Laboratory of Preclinical Study for New Drugs of Gansu Province, Lanzhou University, Lanzhou, 730000, China.

出版信息

Org Lett. 2010 Apr 2;12(7):1544-7. doi: 10.1021/ol1002829.

DOI:10.1021/ol1002829

PMID:20205429

Abstract

The first doubly stereocontrolled organocatalytic asymmetric aldol reaction of alpha-isothiocyanato imides with alpha-ketoesters by using rosin-derived tertiary amine-thiourea under low ligand loading to form cyclic thiocarbamates bearing quaternary stereogenic centers with high levels of enantio- and diastereoselectivity (up to 99% ee, and 97:3 dr) is presented. This reaction provides a convenient doubly stereocontrolled method to access synthetic useful multiply substituted cyclic thiocarbamates with high optical purity.

摘要

本文报道了松香衍生的叔胺-硫脲在低配体负载下，首次实现了α-异硫氰酸根亚胺与α-酮酯的首例双重对映体控制的有机催化不对称Aldol 反应，形成了含有季立体中心的环状硫代氨基甲酸酯，具有高对映选择性和非对映选择性（高达 99%ee，97:3dr）。该反应为获得具有高光学纯度的合成有用的多取代环状硫代氨基甲酸酯提供了一种方便的双重对映体控制方法。