DIOXIRANE MEDIATED STEROIDAL ALKENE EPOXIDATIONS AND OXYGEN INSERTION INTO CARBON-HYDROGEN BONDS

被引：53

作者：

MARPLES, BA ^{[1
]}

MUXWORTHY, JP ^{[1
]}

BAGGALEY, KH ^{[1
]}

机构：

[1] SMITHKLINE BEECHAM PHARMACEUT,BETCHWORTH RH3 7AJ,SURREY,ENGLAND

来源：

TETRAHEDRON LETTERS | 1991年 / 32卷 / 04期

关键词：

D O I：

10.1016/S0040-4039(00)79489-5

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Dioxiranes generated in situ from a range of ketones afforded the 5,6-epoxides in high yield from cholesterol or its acetate. The alpha:beta ratio was close to 1 in contrast to that observed for peroxyacids (ca. 4). 4,4-Dimethylcholesterol and its acetate were not epoxidised but were oxidised respectively to the 3,7-dioxo- and the 7-oxo-derivative respectively with dimethyldioxirane. Oxidations of steroidal alcohols were shown to proceed via an oxygen insertion mechanism by use of O-18-labelled substrates and 5-alpha-cholestan-3-alpha-ol was oxidised more quickly (> 1.5 x) than its 3-beta-epimer.

引用

页码：533 / 536

页数：4

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