Summary A number of 1 a, 3~-dihydroxy-A5-steroids of the cholestane,(20S)-20- methylpregnane (23, 24-dinorcholane), pregnane and androstane series were synthesized from common steroidal precursors. A process originally reported by Barton et al., based on 1, 4, 6-trien-3-ones as intermediates, was used for the introduction of the 1 a-hydroxyl function. The last step of this process, consisting of lithium/ammonia reduction of 1 a, 2a- ...