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化学学报
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化学学报 ›› 2011, Vol. 69 ›› Issue (19): 2272-2280. 上一篇    下一篇

研究论文

16S,20S-环氧孕甾-3S-醇乙酸酯的合成及其区域选择性环氧开环取代反应

韩军1，林静容*<,1，金荣华1，田伟生*,1,2   

  1. (1上海师范大学资源化学实验室 上海 200234)
    (2中国科学院上海有机化学研究所 上海 200032)
  • 投稿日期:2011-03-13 修回日期:2011-05-04 发布日期:2011-05-27
  • 通讯作者: 林静容 E-mail:jrlin@shnu.edu.cn
  • 基金资助:

    上海市教育委员会科研创新项目;上海师范大学一般科研项目

Synthesis of 16S,20S-Epoxypregnane-3S-ol Acetate and Its Regioselective Epoxide-opening Substitution

Han Jun1 Lin Jingrong*,1 Jin Ronghua1 Tian Weisheng*,1,2   

  1. (1 Laboratory of Resource Chemistry, Shanghai Normal University, Shanghai 200234)
    (2 Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032)
  • Received:2011-03-13 Revised:2011-05-04 Published:2011-05-27
  • Contact: LIN JingRong E-mail:jrlin@shnu.edu.cn
  • Supported by:

    The project supported by Innovation Program of Shanghai Municipal Education Commission

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提供了一种将剑麻皂甙元降解产物孕甾三醇转化为16S,20S-环氧孕甾-3S-醇乙酸酯(4b)的合成方法, 并系统地考察了其在不同条件下的环氧开环反应. 研究发现16S,20S-环氧孕甾-3S-醇乙酸酯可选择性地被转化为20R-溴代孕甾- 3S,16S-二醇二乙酸酯、20R-溴代孕甾-3S,16S-二醇-3-乙酸酯、20R-氯代孕甾-3S,16S-二醇二乙酸酯、20R-碘代孕甾- 3S,16S-二醇-3-乙酸酯和孕甾-3S,16S,20R-三醇-3-乙酸酯等化合物. 这些环氧开环反应的条件和结果为合成具有潜在药用价值的合成中间体提供了新思路, 也为具有不对称环氧丁烷结构的甾体化合物提供环氧开环方法.

关键词: 剑麻皂甙元, 孕甾三醇, 16S,20S-环氧孕甾-3S-醇乙酸酯, 环氧开环, 合成

A synthetic method of 16S,20S-epoxypregnane-3S-ol acetate (4b) from pregnane-3S,16S, 20S-triol was developed. Then the epoxide-opening reaction of 4b was investigated under different conditions. The research results showed that 16S,20S-epoxypregnane-3S-ol acetate was chemo-selectively converted into 20R-bromopregnane-3S,16S-diol diacetate, 20R-bromopregnane-3S,16S-diol-3-acetate, 20R-chloropregnane-3S,16S-diol diacetate, 20R-iodopregnane-3S,16S-diol-3-acetate and pregnane-3S, 16S,20R-triol-3-acetate. These results not only provided new synthetic intermediates for the syntheses of steroidal drugs and natural steroids, but also presented epoxide-opening methods of steroids with an asymmetric oxetane ring.

Key words: tigogenin, pregnane-3S,16S,20S-triol, 16S,20S-epoxypregnane-3S-ol acetate, epoxide-opening, synthesis