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Microbial hydroxylation of steroids provides a useful mild synthetic method for obtaining access to rare steroids [71]. The cyclopropane ring of the 3 a -5-cyclosteroids is sensitive to a variety of reagents limiting many chemical reactions. The fission of a cyclopropane ring in the presence of an adjacent radical has
provided a probe for enzyme mechanism [72]. Incubation of 6b-hy-droxy-3 a , 5-cycloandrostan-17-one (145) with C. aphidicola [73]for 8 days yielded six metabolites that were identified as14 a -hydroxy-3 a ,5-cycloandrostane-6, 17-dione (145), 3b, 14 a -dihydroxyandrost-5-en-17-one (146), 6b, 14 a -dihydroxy-3 a ,
5-cycloandrostan-17-one (147), 3b, 7 a -dihydroxyandrost-5-en-17-one (148), 3b, 7b-dihydroxyandrost-5-en-17-one (149) and 3b, 5 a , 6b-trihydroxyandrostan-17-one (150) (Scheme 23). Simi-larly, incubation of 3 a , 5-cycloandrostane-6, 17-dione (151) with C. aphidicola [73] yielded 145 and 2 a -hydroxy-3 a , 5-cycloandros-tane-6, 17-dione (152), while 3 a , 5-cycloandrost-6-en-17-one (153) afforded 148 and 6b, 7 a -dihydroxy-3 a , 5-cycloandrostane-17-one (154) with the same fungus [73]. These microbial conversions are shown in Scheme 23.

a为α,   b 为β

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bxzc123: 金币+75, 翻译EPI+1, ★★★很有帮助 2015-04-27 19:08:00
甾族化合物的微生物羟基化作用为获得稀少的甾族化合物提供了一种有用的温和合成方法。3 a - 5 -环甾族化合物的环丙烷环对各种限制许多化学反应的试剂敏感。在一个相邻基团存在下环丙烷环的开环为酶作用机理提供了一个探针[72]。 用头孢霉属真菌C. aphidicola [73]培育6b-羟基-3a, 5-环雄甾-17-酮(145)8天得到六种代谢产物,分别鉴别为14 a -羟基-3 a,5-环雄甾-6、17-二酮(145)、3b, 14 a-二羟基雄甾-5-烯-17-酮( 146)、6b, 14 a-二羟基-3 a,5-环雄甾-17-(147)、 3b, 7 a -二羟基雄甾-5-烯-17-酮( 148)、3b,7b-二羟基雄甾-5-烯-17-酮( 149)和3b, 5 a, 6b-三羟基雄甾-17-酮(150)图23)。Simi-larly,用头孢霉属真菌C. aphidicola [73]培育3 a,5-环雄甾- 6,17-二酮(151)得到145和2 a -羟基- 3 a, 5-环雄甾-6, 17-二酮(152),而用同样的真菌[73]由3 a, 5 -环雄甾-6-烯-17-酮(153)得到了148和6b,7a-二羟基-3 a,5-环雄甾-17-酮(154)。这种微生物引起的转化作用具体请见图23。
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