THE SYNTHESIS OF A-HOMO-B-NORANDROSTANES - THE EFFECT OF A HYDROXYL ON THE COURSE OF HYDROGENATION OF THE DELTA(9)-DOUBLE BOND

Acetolysis of 6 beta-mesyloxy-5-methyl-19-nor-5 beta-steroids (e.g. 10 ) was proved to yield 4a-homo-7,19-dinor compounds (e.g. 9) with a hyd roxy group in the position 4a alpha. Hydrogenation of these compounds affords 9 beta,10 beta-dihydro derivatives (e.g. 12) predominantly, co rresponding 9 alpha,10 alpha isomers (e.g. 13) are only formed in low yields. This sequence was used for the synthesis of analogues of andro gen hormones 4a alpha-hydroxy-4a beta-methyl-4a-homo-7,19-dinor-5 alph a,9 beta,10 beta-androstane-3,17-dione (27), 4a alpha,17 beta-dihydrox y-4a beta,17 alpha-dimethyl-4a-homo-7,19-dinor-5 alpha,9 beta,10 beta- androstan-3-one (28) and 4a alpha,17 beta-dihydroxy-4a beta-methyl-4a- homo-7,19-dinor-5 alpha,9 beta,10 beta-androstan-3-one (29).