合成路线1

A different strategy for preparing the target 6-methylated steroid nucleus was based on the conjugate addition of an organocuprate reagent to a dienone. The intermediate hydroxy enone (IV) was acylated with isopropenyl acetate to produce the bis-acetate (XII). Bromination of (XII) with N-bromosuccinimide, followed by dehydrohalogenation with Li2CO3 and LiBr in refluxing DMF, gave rise to dienone (XIII). Conjugate addition of methyllithium to (XIII) in the presence of CuI afforded the methylated compound (XIV). Aromatization of the cyclohexenone system was achieved by oxidation with CuCl2. Subsequent acetate ester hydrolysis under basic conditions generated diol (XV), which was converted to the bis-mesylate (XVI) upon treatment with methanesulfonyl chloride and Et3N. Displacement of the aliphatic mesylate with vanillic acid diethylamide (VII) yielded ether (XVII). Then, simultaneous amide reduction and reductive cleavage of the aryl mesylate with LiAlH4 provided the title compound.