通过环丙醇中间体从酯类和烯烃立体选择性合成α-甲基和α-烷基酮。

Stereoselective synthesis of α-methyl and α-alkyl ketones from esters and alkenes via cyclopropanol intermediates.

作者信息

Barysevich Maryia V, Kazlova Volha V, Kukel Aliaksandr G, Liubina Aliaksandra I, Hurski Alaksiej L, Zhabinskii Vladimir N, Khripach Vladimir A

机构信息

Laboratory of Steroids, Institute of Bioorganic Chemistry, National Academy of Sciences of Belarus, Kuprevich 5/2, Minsk 220141, Belarus.

出版信息

Chem Commun (Camb). 2018 Mar 13;54(22):2800-2803. doi: 10.1039/c8cc00888d.

DOI:10.1039/c8cc00888d

PMID:29489006

Abstract

Alkenes bearing a stereocenter in the allylic position were found to undergo Kulinkovich hydroxycyclopropanation with good diastereoselectivity. For the isomerization of the resulting cyclopropanols to diastereomerically enriched α-methyl ketones, a new mild regioselective method has been developed. A sequence of stereoselective cyclopropanation and cyclopropanol ring opening was successfully employed for the construction of the C20 stereocenter in steroids.

摘要

发现烯丙基位置带有立体中心的烯烃能以良好的非对映选择性进行库林科维奇羟基环丙烷化反应。对于将所得环丙醇异构化为非对映体富集的α-甲基酮，已开发出一种新的温和区域选择性方法。立体选择性环丙烷化和环丙醇开环的序列已成功用于甾体中C20立体中心的构建。