The invention relates to processes for preparing 3α-O-linked steroids including 3α-O-linked-androst-5-ene steroids and 3α-O-linked-5α-androstane steroids. In one process a 3α,4α-epoxy androst-5-en-17-one is predominately reduced at the epoxy moiety wherein reduction of the 3α,4α epoxy functional group occurs preferentially at position C4 with retention of configuration at position C3 to provide a 3α-O-linked-androst-5-ene steroid. In another process, conditions are provided for inversion of configuration of a 3β-hydroxy-androst-5-ene steroid by the Mitsunobu reaction to provide a 3α-O-linked-androst-5-ene steroid with reduced amounts of 3α,5α-cycloandrostane side-product impurities.
