迭代直接羟醛缩合策略制备聚丙酸盐：(-)-membrenone A 和 B 的对映选择性全合成。

Iterative direct aldol strategy for polypropionates: enantioselective total synthesis of (-)-membrenone A and B.

机构信息

Institute of Microbial Chemistry (BIKAKEN), Tokyo , 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo 141-0021, Japan.

出版信息

Org Lett. 2014 Oct 17;16(20):5301-3. doi: 10.1021/ol5024932. Epub 2014 Sep 26.

Abstract

An iterative direct aldol reaction using a C3 propionate unit as an aldol donor offers expeditious access to polyketide assembly in a highly diastereo- and enantioselective manner. An all-syn polyketide array with four consecutive stereogenic centers was efficiently constructed by an aldol reaction of thiopropionamide via soft Lewis acid/hard Brønsted base cooperative catalysis. This iterative aldol strategy led to an enantioselective synthesis of (-)-membrenone A and B.

摘要

采用 C3 丙酸酯单元作为羟醛供体的迭代直接羟醛反应以高度非对映选择性和对映选择性方式提供了快速进入聚酮体组装的途径。通过软路易斯酸/硬布朗斯台德碱协同催化的硫代丙酰胺的羟醛反应，有效地构建了具有四个连续立体中心的全 syn 聚酮体阵列。这种迭代羟醛策略导致了(-)-membrenone A 和 B 的对映选择性合成。