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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.
The synthetic route to construct 6β, 7β-methylene structure in steroid molecule was designed.Using 4,6-androst-3,17-dione as starting material, sodium borohydride, Benzoic acid epoxidation, lithium aluminum hydride reduction ring opening, Simmons-Smith addition and other 4-step reaction to obtain the target compound 6β, 7β-methylene androsta-3β, 5β, 17-triol intermediate 4β, 5β-epoxy-6-androstene-3β, 17-diol was removed by C-4-O reduction to give the cis-6-androstene-3β, 5β, 17-triol in 93% yield, To C-5-O cleavage products, so that the 5β-hydroxy-6-steene structure required for the stereospecific orientation-oriented Simmons-Smith addition was efficiently obtained. The intermediates and target compounds were characterized by IR, 1H NMR Spectroscopy, mass spectrometry and elemental analysis confirmed its chemical structure.