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有机化学
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有机化学 ›› 2011, Vol. 31 ›› Issue (03): 379-382. 上一篇    下一篇

研究简报

基于乙烯基环氧构建雄甾6β,7β-亚甲基的方法

贺诗华*,1，王春婷2   

  1. (1西安科技大学化学与化工学院 西安 710054)
    (2第四军医大学神科学研究所 西安 710032)
  • 收稿日期:2010-03-23 修回日期:2010-07-08 发布日期:2010-10-25
  • 通讯作者: 贺诗华 E-mail:heshihua@xust.edu.cn
  • 基金资助:

    西安科技大学科研培育基金

A Vinyl Epoxide Based Approach to 6β,7β-Methylene in Androstanes

He Shihua*,1 Wang Chunting2   

  1. (1 College of Chemistry and Chemical Engineering, Xi an University of Science and Technology, Xi an 710054)
    (2 Institute of Neuroscience, Forth Military Medicine University, Xi an 710032)
  • Received:2010-03-23 Revised:2010-07-08 Published:2010-10-25

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设计了简便构建甾体分子中6β,7β-亚甲基结构的合成路线. 以4,6-雄二烯-3,17-二酮为起始原料, 依次经硼氢化钠还原、间氯过氧苯甲酸环氧化、氢化铝锂还原性开环、Simmons-Smith加成等4步反应得到目标结构化合物6β,7β-亚甲基雄甾-3β,5β,17-三醇. 中间体4β,5β-环氧-6-雄烯-3β,17-二醇经C-4-O还原开环得到顺式产物6-雄烯-3β,5β,17-三醇, 产率93.0%, 没有检测到C-5-O裂解产物, 从而高效地得到了高立体选择性定位导向Simmons-Smith加成所需的5β-羟基-6-甾烯结构. 中间体和目标物经红外光谱、核磁共振氢谱、质谱及元素分析确证了其化学结构.

关键词: 环丙化, 6β,7β-亚甲基甾体, 环氧开环, Simmons-Smith加成, 氢化铝锂还原

The construction of 6β,7β-methylene in steroids has received considerable attention. A facile approach to the 6β,7β-methylene unit was reported and the target compound 6β,7β-methylene androsta- 3β,5β,17-triol was conveniently synthesized from 4,6-androstodiene-3,17-dione by reduction with sodium borohydride, epoxidation with meta-chloroperbenzoic acid, reductive ring cleavage with lithium-aluminum hydride, and Simmons-Smith addi-tion in series. The reductive ring cleavage of the 4β,5β-epoxy ring in steroid came out to be C-4-O cleavage to give cis product 6-androstene-3β,5β,17β-triol in the yield of 93.0%, resisting to C-5-O cleavage, which is the key mechanism to afford the needed unit 5β-hydroxyl-6-ene for highly β-stereoselective Simmons-Smith addition to produce the target unit 6β,7β-methylene. The chemical structures of intermediates and target product were characterized by IR, 1H NMR, MS techniques, and elemental analysis.

Key words: cyclopropanation, 6β,7β-methylen-steroid, epoxide cleavage, Simmons-Smith addition, Li-AlH4 reduction