甾醇合成。一种新型的α,β-不饱和甾体环氧化物的还原重排反应；5α-胆甾-8(14)-烯-3β,15α-二醇的新化学合成方法。

Sterol synthesis. A novel reductive rearrangement of an alpha,beta-unsaturated steroidal epoxide; a new chemical synthesis of 5alpha-cholest-8(14)-en-3beta, 15alpha-diol.

作者信息

Parish E J, Schroepfer G J

出版信息

Chem Phys Lipids. 1977 Apr;18(3-4):258-66. doi: 10.1016/0009-3084(77)90013-5.

Abstract

Reduction of 3beta-benzoyloxy-14alpha,15alpha-epoxy-5alpha-cholest-7-ene with either lithium triethylboro-hydride or lithium aluminum hydride (4 molar excess) gave 5-alpha-cholest-8(14)-en-3beta,15alpha-diol in high yield. Reduction of the epoxy ester with lithium triethylborodeuteride or lithium aluminum deuteride (4 molar excess) gave [7alpha-2-H]-5alpha-cholest-8(14)-en-3beta,15alpha-diol. Reduction of 2beta-benzoyloxy-14alpha,15alpha-epoxy-5alpha-cholest-7-ene with a large excess (24 molar excess) of lithium aluminum hydride gave, in addition to the expected 5alpha-cholest-8(14)-en-3beta,15alpha-diol, a significant yield (33%) of 5alpha-cholest-8(14)-en-3beta-o1. Reduction of the epoxy ester with a large excess (24 molar excess) of lithium aluminum deuteride gave [7alpha-2H]-5alpha-cholest-8(14)-en-3beta,15alpha-diol and 5alpha-cholest-8(14)-en-3beta-o1 which contained two atoms of stably bound deuterium.

摘要

用三乙基硼氢化锂或氢化铝锂（4摩尔过量）还原3β-苯甲酰氧基-14α,15α-环氧-5α-胆甾-7-烯，可高产率得到5α-胆甾-8(14)-烯-3β,15α-二醇。用三乙基硼氘化锂或氘代氢化铝锂（4摩尔过量）还原环氧酯，得到[7α-2-H]-5α-胆甾-8(14)-烯-3β,15α-二醇。用大量过量（24摩尔过量）的氢化铝锂还原2β-苯甲酰氧基-14α,15α-环氧-5α-胆甾-7-烯，除了预期的5α-胆甾-8(14)-烯-3β,15α-二醇外，还以可观的产率（33%）得到了5α-胆甾-8(14)-烯-3β-醇。用大量过量（24摩尔过量）的氘代氢化铝锂还原环氧酯，得到[7α-2H]-5α-胆甾-8(14)-烯-3β,15α-二醇和含有两个稳定结合氘原子的5α-胆甾-8(14)-烯-3β-醇。