光学活性(+)-3-甲氧基-7α-甲基-17α-氰甲基-17β-羟基-135(10)-雌甾三烯的合成

The Synthesis of (+)-3-Methoxy-7α-methyl-17α-Cyanomethyl-17β-hydroxy-1, 3,5- (10) -Estratriene

(+)-3-甲氧基-7α-甲基-17α-氰甲基-17β-羟基-1,3,5(10)-雌甾三烯12是通过从1与2的缩合物经氢化、环合、锂氨还原、去叔丁基、氧化、次甲基化以及开环氧共七步反应合成而得.

The titled compound 12 waa obtained through aeven stepa using the compound 3 as starting material. Hydrogenated compound 4 obtained from 3 was cyclized with H_2SO_4 to the compound 6, hydrogenation of which gave a mixture of the compound 7 and 8. The compound 8 was also secured directly by reduction of 6 with Li and liq. NH_3. Deprotection of the compound 8 by HCl gave the compound 9 which was oxidized to the compound 10. Introducing the methylene group by dimethyl oxosulfonium methylide at 17-ketone in the compound 10 gave the epoxide 11 which was cleavaged to the titled compound 12 by NaCN.