利用薯蓣皂甙元完整骨架形式合成1α,25-二羟基维生素D_3  

Formal Synthesis of 1α,25-Dihydroxyvitamin D_3 by Utilizing the Intact Skeleton of Diosgenin

作　　者：林静容[1] 王玉春[1] 许启海[2] 金荣华[1] 田伟生[1] 

机构地区：[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

出　　处：《化学学报》2007年第16期1685-1692,共8页Acta Chimica Sinica

摘　　要：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5C-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.　（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.

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 

分 类 号：TQ466.4[化学工程—制药化工]