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化学学报
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化学学报 ›› 2007, Vol. 65 ›› Issue (16): 1685-1692. 上一篇    下一篇

研究论文

利用薯蓣皂甙元完整骨架形式合成1α,25-二羟基维生素D3

林静容1, 王玉春1, 许启海2, 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:2007-03-26 修回日期:2007-04-25 发布日期:2007-08-28
  • 通讯作者: 田伟生

Formal Synthesis of 1α,25-Dihydroxyvitamin D3 by Utilizing the Intact Skeleton of Diosgenin

LIN Jing-Rong1; WANG Yu-Chun1; XU Qi-Hai2; JIN Rong-Hua1; TIAN Wei-Sheng*,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:2007-03-26 Revised:2007-04-25 Published:2007-08-28
  • Contact: TIAN Wei-Sheng

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首次利用薯蓣皂甙元的完整骨架经16步反应以7.6%的总收率合成了骨化三醇(1α,25-二羟基维生素D3)的光化反应前体. 3-苄基保护的薯蓣皂甙元经还原开E/F环产生3,16,26-胆甾三醇-3-苄醚(5). 除去化合物5 C-16羟基后, 其C-26羟基经消除和羟基化反应转移到C-25位. 目标分子A/B环结构单元通过薯蓣皂甙元A/B环的官能团转化被构筑. 按照已知的光化反应, (1S,3R)-胆甾-5,7-二烯-1,3,25-三醇能被转化成为1α,25-二羟基维生素D3.

关键词: 1α,25-二羟基维生素D3, 薯蓣皂甙元, (1S,3R)-胆甾-5,7-二烯-1,3,5-三醇, 资源化学

(1S,3R)-Cholesta-5,7-diene-1,3,25-triol, a photochemical reaction precursor for the preparation of 1α,25-dihydroxyvitamin D3 , was synthesized by utilizing the intact skeleton of diosgenin in 16 steps in 7.6% overall yield. The reductive E/F ring opening of 3-benzyloxy-diosgenin produced 3,16,26-cholesteratriol benzyl ether 5. The C-26 hydroxy group was shifted to C-25 through the elimination and hydroxylation after the selective removal of C-16 hydroxyl group in 5. The A/B structural unit of the target molecule was constructed by the functional transformation of the A/B ring of diosgenin. (1S,3R)-Cholesta-5,7-diene-1,3,25-triol can be converted into 1α,25-dihydroxyvitamin D3 according to the known photochemical reaction.

Key words: 1α,25-dihydroxyvitamin D3, diosgenin, (1S,3R)-cholesta-5,7-diene-1,3,25-triol, resource chemistry