Batist J N, Barendse N C, Marx A F
Research and Development, Gist-brocades, Delft, The Netherlands.
Steroids. 1990 Mar;55(3):109-13. doi: 10.1016/0039-128x(90)90005-v.
Two methods to produce the 17-cyanohydrin, using potassium cyanide in acetic acid/methanol or acetone cyanohydrin with aqueous sodium hydroxide, were followed with 9 alpha-hydroxyandrost-4-ene-3,17-dione, both providing 17 beta-cyano-9 alpha,17 alpha-dihydroxyandrost-4-en-3-one. The selectivity of one of these methods, that which uses acetone cyanohydrin, is not in agreement with a comparable reaction with the 9 alpha-unsubstituted androst-4-ene-13,17-dione to give the 17 alpha-cyano-17 beta-hydroxy product, as reported in the literature and confirmed by us. The 9 alpha-hydroxy and 17 alpha-hydroxy groups were used for the regioselective introduction of 9(11)- and 16(17)-double bonds by dehydrating 17 beta-cyano-9 alpha,17 alpha-dihydroxyandrost-4-en-3-one under different conditions.
采用两种方法制备17-氰醇，一种是在乙酸/甲醇中使用氰化钾，另一种是用丙酮氰醇与氢氧化钠水溶液，以9α-羟基雄甾-4-烯-3,17-二酮为原料，两种方法均得到17β-氰基-9α,17α-二羟基雄甾-4-烯-3-酮。其中一种方法，即使用丙酮氰醇的方法，其选择性与文献报道并经我们证实的9α-未取代雄甾-4-烯-13,17-二酮生成17α-氰基-17β-羟基产物的类似反应不一致。通过在不同条件下使17β-氰基-9α,17α-二羟基雄甾-4-烯-3-酮脱水，利用9α-羟基和17α-羟基进行区域选择性引入9(11)-和16(17)-双键。
