硫代酰胺的直接催化不对称醛醇缩合反应：立体控制的 1,3-多醇合成。

Direct catalytic asymmetric aldol reactions of thioamides: toward a stereocontrolled synthesis of 1,3-polyols.

机构信息

Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.

出版信息

J Am Chem Soc. 2009 Dec 30;131(51):18244-5. doi: 10.1021/ja909758e.

PMID:19994862

Abstract

A direct catalytic asymmetric aldol reaction of thioamides with a soft Lewis acid/hard Brønsted base cooperative catalytic system comprising (R,R)-Ph-BPE/[Cu(CH(3)CN)(4)]PF(6)/LiOAr is described. Highly chemoselective deprotonative activation of thioamides allows for a direct aldol reaction of alpha-nonbranched aliphatic aldehydes, which are susceptible to self-condensation. Facile reduction of the thioamide functionality and a catalyst-controlled second aldol reaction provides 1,3-diols in a highly stereoselective manner.

摘要

描述了一种包含（R,R）-Ph-BPE/[Cu（CH（3）CN）（4）]PF（6）/LiOAr 的软路易斯酸/硬布朗斯特碱协同催化体系的硫代酰胺与醛的直接不对称Aldol 反应。硫代酰胺的高化学选择性去质子化活化作用使得易于自身缩合的α-非支链脂肪醛能够直接进行Aldol 反应。硫酰胺官能团的还原以及催化剂控制的第二次Aldol 反应以高度立体选择性的方式提供了 1,3-二醇。