A-失碳雄甾-3-羰基-16β-甲酸甲酯的合成

The systhesis of A-norandrostane-3-oxo-16β-carboxylate

摘要:

以3-羰基-4-雄甾烯-17β-甲酸甲酯为原料，经Beayer-Villger氧化、甲醇钠促进的缩环重排和脱羰两步独立的化学操作，合成了A-失碳雄甾-3-羰基-16β-甲酸甲酯，总收率为39.2 %。通过控制氧化剂间氯过氧苯甲酸（m-CPBA）的用量、使用Lewis酸ZnCl2，Baeyer-Villiger氧化产物3-羰基-4-氧杂-5-雄甾烯-17β-甲酸甲酯的收率高达92.3 %； 3-羰基-4-氧杂-5-雄甾烯-17β-甲酸甲酯在干燥四氢呋喃中，经甲醇钠作用重排为A环缩环的β-羰基醛中间体，再由NaOH水溶液处理脱羰后得A-失碳雄甾-3-羰基-16β-甲酸甲酯，收率为42.5 %。该方法为制备A-失碳甾体化合物提供了一条新颖的合成途径。

Abstract:

A-norandrostane-3-oxo-16β-carboxylate was synthesized from 3-oxo-4-androstene-17β-carboxylate by Beayer-Villger oxidation and two independent chemical operation,which were sodium methoxide promoted ring contraction rearrangement and decarbonylation, the total yield was 39.2 %.By controlling the amount of oxidant metachloroperbenzoic acid (m-CPBA) and using ZnCl2 as Lewis acid,the yield of the product of Beayer-Villger oxidation 3-oxo-4-androstene-17β-carboxylate was 92.3 %. 3-oxo-4-androstene-17β-carboxylate was converted to A ring constracted β-oxo aldehyde in the effect of sodium methoxide in dry tetrahydrofunan,,then it was decarbonylated by NaOH aqueous solution ,the product A-norandrostane-3-oxo-16β-carboxylate was prepared，its yield was 42.5 %.The method offers a new and unique synthetic route for preparation of A-norsteroidal compound.