Synthesis of Epimeric 2-d1-5β-Pregnane-3, 11, 20-triones
Synthesis of Epimeric 2-d1-5β-Pregnane-3, 11, 20-triones
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差向异构体 2-d1-5β-Pregnane-3, 11, 20-三酮的合成
DOI：
10.1248/cpb.27.1864
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发表时间：
1979
期刊：
影响因子：
--
通讯作者：
T. Nambara
中科院分区：
文献类型：
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作者：
S. Ikegawa;Y. Hino;M. Sunagawa;T. Nambara
为了阐明5β-甾烷-3，11，20-三酮微生物转化为Δ1-不饱和化合物过程中C-2位失氢的立体化学，进行了C-2位差向异构氘代底物的立体定向合成。以易得的11α-羟基孕酮为原料，经两条合成路线得到关键中间体5β-孕甾-2-烯-11 α，20β-二醇二乙酸酯。2β，3β-环氧化物与氘化铝锂的反式双轴开环得到2α-d1-3β-醇。Δ2-烯烃的氘代硼化和随后的有机硼烷的氧化得到2α-d1-3β-醇。用三氧化铬-吡啶络合物氧化，差向异构体2-d1-5β-甾烷-3 β，11α，20β-三醇转化为所需的2-d1-5β-甾烷-3，11，20-三酮。
In order to clarify the stereochemistry of hydrogen loss from the C-2 position during microbial transformation of 5β-pregnane-3, 11, 20-trione into the Δ1-unsaturated compound, the stereospecific synthesis of epimeric C-2 deuterated substrates has been carried out. A key intermediate, 5β-pregn-2-ene-11α, 20β-diol diacetate, was obtained from the readily available 11α-hydroxyprogesterone through two synthetic routes. The trans-diaxial opening of the 2β, 3β-epoxide with lithium aluminum deuteride provided the 2α-d1-3β-ol. Deuterioboration of the Δ2-olefin and subsequent oxidation of the organoborane afforded the 2α-d1-3β-ol. On oxidation with chromium trioxide-pyridine complex, the epimeric 2-d1-5β-pregnane-3β, 11α, 20β-triols were converted to the desired 2-d1-5β-pregnane-3, 11, 20-triones.