SYNTHESES OF 21-HYDROXY-11,19-OXIDOPREGN-4-ENE-3,20-DIONE AND 21-HYDROXY-6,19-OXIDOPREGN-4-ENE-3,20-DIONE

The 21-hydroxy analogues of 11,19-oxidoprogesterone and 6,19-oxidoprog esterone have been synthesized from readily available materials. Hydro xylation at C-21 was effected with iodosobenzene (from phenyliodosodia cetate and methanolic potassium hydroxide) on a 20-ketopregnane. For t he 11,19-oxido derivative, the hydroxylation was carried our on a prec ursor containing the oxide-bridge. This approach was not adequate for the 6,19-oxido steroid due to the very low yields encountered; hence i n the latter case the order of introduction of the C-21 functionality and the oxide-bridge was reversed.