Pouzar V, Slavíková T, Cerńy I
Institute of Organic Chemistry and Biochemistry, Academy of Sciences of the Czech Republic, Prague, Czech Republic.
Steroids. 1998 Sep;63(9):454-8. doi: 10.1016/s0039-128x(98)00047-6.
The title compound was prepared in 11 steps from 17,17-ethylenedioxy-19-hydroxyandrost-5-en-3 beta-yl acetate. After tert-butyldimethylsilyl protection of the 19-hydroxyl group, a 7-oxo group was introduced by oxidation with 3,5-dimethylpyrazole-chromium trioxide complex, and then selectively reduced with L-Selectride to give a 7 alpha-hydroxy derivative. This partially protected triol was acetylated and desilylated to 3,7-diacetate. Subsequent oxidation with pyridine-chromium trioxide complex gave 19-aldehyde, which was transformed into the corresponding protected 19-(O-carboxymethyl)oxime. Successive ketal cleavage, deacetylation, and methyl ester splitting gave the final (19E)-3 beta,7 alpha-dihydroxy-17-oxoandrost-5-en-19-al 19-(O-carboxymethyl)oxime, designed as a hapten for 7 alpha-hydroxydehydroepiandrosterone immunoassays.
标题化合物由17,17 - 亚乙基二氧基 - 19 - 羟基雄甾 - 5 - 烯 - 3β - 基乙酸酯经11步反应制备而成。19 - 羟基用叔丁基二甲基甲硅烷基保护后，用3,5 - 二甲基吡唑 - 三氧化铬配合物氧化引入7 - 氧代基团，然后用L - 选择氢化物选择性还原得到7α - 羟基衍生物。将这种部分保护的三醇乙酰化并脱硅基得到3,7 - 二乙酸酯。随后用吡啶 - 三氧化铬配合物氧化得到19 - 醛，将其转化为相应的保护的19 - (O - 羧甲基)肟。依次进行缩酮裂解、脱乙酰化和甲酯裂解得到最终的(19E) - 3β,7α - 二羟基 - 17 - 氧代雄甾 - 5 - 烯 - 19 - 醛19 - (O - 羧甲基)肟，设计用作7α - 羟基脱氢表雄酮免疫测定的半抗原。
