Reeder A Y, Joannou G E
Department of Metabolic Mass Spectrometry, Royal Prince Alfred Hospital, New South Wales, Sydney, Australia.
Steroids. 1996 Jan;61(1):22-6. doi: 10.1016/0039-128x(95)00171-l.
A successful approach to the synthesis of 3 beta,15 beta-dihydroxy-5-androsten-17-one (14d) has been developed using trichloroethoxy ethers as intermediates in the synthesis of the corresponding alcohols. 3 beta-Methoxymethoxy-5,15-androstadien-17-one (10c) was prepared by a selenation/dehydroselenation strategy from 3 beta-methoxymethoxy-5-androsten-17-one (14c). Base-catalyzed reaction of trichloroethanol with 10c gave 3 beta-methoxymethoxy-15 beta-trichloroethoxy-5-androsten-17-one (14g). Under the same conditions, 3 beta-acetoxy-5,15-androstadien-17-one (10b) gave 3 beta-hydroxy-15 beta-trichloroethoxy-5-androsten-17-one (14f) which was characterized after conversion to 14g. Cleavage of the trichloroethoxy group in 14f with zinc or zinc/copper couple gave 14d. The acid-catalyzed hydrolysis of 17,17-ethylenedioxy-5,15-androstadien-3 beta-ol (15) gave 3 beta-hydroxy-5,15-androstadien-17-one (10a) as the major product along with 14d. However, addition of water to 10a in the presence of acid gave the desired product 14d in poor yield (15%).
已开发出一种成功合成3β,15β - 二羟基 - 5 - 雄甾烯 - 17 - 酮（14d）的方法，该方法使用三氯乙氧基醚作为中间体来合成相应的醇。3β - 甲氧基甲氧基 - 5,15 - 雄甾二烯 - 17 - 酮（10c）是通过硒化/脱氢硒化策略由3β - 甲氧基甲氧基 - 5 - 雄甾烯 - 17 - 酮（14c）制备而成。三氯乙醇与10c在碱催化下反应生成3β - 甲氧基甲氧基 - 15β - 三氯乙氧基 - 5 - 雄甾烯 - 17 - 酮（14g）。在相同条件下，3β - 乙酰氧基 - 5,
