Asymmetric synthesis of 3β-acetoxy-17,17-ethylendioxy-15β, 16β-methylene-5-androsten-7β-ol①
来源期刊：中南大学学报(英文版)2004年第1期
论文作者：刘丰良 周康根 阳卫军 杨喜云
文章页码：59 - 62
Key words：3β-acetoxy-15β, 16β-methylene-5-androsten-17-one; asymmetric synthesis; 3β-acetoxy-17, 17-ethylen-dioxy-15β,16β-methylene-5-androsten-7β-ol
Abstract: 3β-acetoxy-17,17-ethylendioxy-15β,16β-methylene-5-androsten-7β-ol(Ⅰ) was prepared by 3 steps from 3β-acetoxy-15β,16β-methylene-5-androsten-17-one (Ⅱ) with overall yield of 52.7%. Thus, interaction of ethylene glycol and material (Ⅱ) gave 3β-acetoxy-17,17-ethylendioxy-15β,16β-methylene-5-androsten (Ⅲ) which was subsequently oxidated and stereoselectively reduced to produce compound(Ⅰ). The normal influencing factors, such as the types of ox-idants and reductives, the mole ratio of reactants, the reaction temperature, and the addition ways of reactants, in oxida-tion and reduction were discussed. The results show that the oxidation rate order is CrO3-C5H5N (1∶1, mole fraction)>CrO3-C5H5N(1∶2)>(C5H5NH)2Cr2O7in terms of the oxidant, the yield of the oxidation becomes higher with increasing the oxidant stoichiometry and raising the reaction temperature. And the optimum condition is that the reaction temperature is at 30℃, andn(Ⅲ)/n(CrO3-C5H5N(1∶2))=1∶20. The yield of the-7βalcohol order with Li[Al(OC(CH3)3)3H] (e.g.78.6%) is more than that with NaBH4(e.g.14.5%) in terms of the reductive agent and the reduction rate decreases in the course of reaction. The compound (Ⅰ) is characterized by IR and MS.
