Wiebe J P, Deline C, Buckingham K D, Dave V, Stothers J B
Steroids. 1985 Jan;45(1):39-51. doi: 10.1016/0039-128x(85)90064-9.
A method for the convenient synthesis of the recently isolated allylic gonadal steroids, 3 alpha-hydroxy-4-pregnen-20-one (3 alpha-dihydroprogesterone; 3 alpha-DHP) and 3 alpha-hydroxy-4-androsten-17-one (3 alpha-HA), was developed using 4-pregnene-3,20-dione (progesterone) and 4-androstene-3,17-dione as substrates and potassium trisiamylborohydride (KS-Selectride) as reducing agent. Similar reactions were also used for the reduction of 5 alpha-pregnane-3,20-dione to 3 alpha-hydroxy-5 alpha-pregnan-20-one (3 alpha-HP). The yields were about 15%, 50%, and greater than 90% for 3 alpha-DHP, 3 alpha-HA and 3 alpha-HP, respectively. Structures of the products, including the 3 beta-isomers and the 17 alpha-epimer, formed in these reactions were determined by NMR and mass spectroscopic methods.
利用4-孕烯-3,20-二酮（孕酮）和4-雄烯-3,17-二酮作为底物，三（三戊基）硼氢化钾（KS-Selectride）作为还原剂，开发了一种便捷合成最近分离出的烯丙基性腺甾体3α-羟基-4-孕烯-20-酮（3α-二氢孕酮；3α-DHP）和3α-羟基-4-雄烯-17-酮（3α-HA）的方法。类似的反应也用于将5α-孕烷-3,20-二酮还原为3α-羟基-5α-孕烷-20-酮（3α-HP）。3α-DHP、3α-HA和3α-HP的产率分别约为15%、50%和大于90%。通过核磁共振（NMR）和质谱方法确定了这些反应中形成的产物结构，包括3β-异构体和17α-差向异构体。
