Chin. J. Org. Chem. ›› 2011, Vol. 31 ›› Issue (03): 379-382. Previous Articles     Next Articles

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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

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