二甲基二氧杂环丙烷在多官能团甾体选择性氧化中的应用。

The application of dimethyldioxirane for the selective oxidation of polyfunctional steroids.

作者信息

Sasaki T, Nakamori R, Yamaguchi T, Kasuga Y, Iida T, Nambara T

机构信息

Department of Chemistry, College of Humanities and Sciences, Nihon University, Setagaya, Sakurajousui, Tokyo 156-8550, Japan.

出版信息

Chem Phys Lipids. 2001 Feb;109(2):135-43. doi: 10.1016/s0009-3084(00)00209-7.

DOI:10.1016/s0009-3084(00)00209-7

PMID:11269933

Abstract

Oxidation and epoxidation reactions of a series of structurally different steroids related to methyl 5 beta-cholanoates having hydroxyl groups and/or double bonds by treatment with dimethyldioxirane (DMDO) are described. Steroidal alcohols, olefines, and unsaturated alcohols and conjugated enones with DMDO were transformed into ketones, epoxides, and epoxy-ketones, respectively, in good isolated yields. The regio- and stereoselectivities for DMDO reaction differing from those observed for organic peracids, tert-butyl hydroperoxide and alkaline hydrogen peroxide are also discussed.

摘要

本文描述了一系列与具有羟基和/或双键的5β-胆酸甲酯相关的结构不同的甾体，通过用二甲基二氧杂环丙烷（DMDO）处理进行氧化和环氧化反应。甾体醇、烯烃、不饱和醇以及与DMDO反应的共轭烯酮分别以良好的分离产率转化为酮、环氧化物和环氧酮。还讨论了DMDO反应的区域选择性和立体选择性，这些选择性与有机过酸、叔丁基过氧化氢和碱性过氧化氢所观察到的不同。