Abstract
The procedure used for the preparation of 1α-hydroxycholesterol from cholesta-1, 4-dien-3-one was applied to 17, 17-ethylenedioxyandrosta-1, 4-dien-3-one and 20, 20-ethylenedioxypregna-1, 4-dien-3-one. The successful results described in this paper serve to provide a basis for evaluation of wide scope of this procedure for the introduction of a hydroxyl group at 1α-position of 3-oxygenated steroid derivatives. The procedure consists of three steps starting from 3-keto-△1, 4-steroids available readily from 3-oxygenated steroids : 1) deconjugation to 3-keto-△1, 5-steroids, 2) reduction with metalhydride to 3β-hydroxy-△1, 5-steroids, and 3) hydroboration to 1α, 3β-dihydroxy-△5-steroids. This paper also includes definite identification of the final and intermediate compounds in the procedure and interpretation of their mass and nuclear magnetic resonance spectroscopic behaviors.
