Each epimers of 2, 3-episulfides of 5β, 25D-spirostane and 17β-hydroxy-5α-androstanes having a methyl group at C-1α, C2, or C3 were synthesized via the corresponding vicinal diaxial thiocyanatohydrins. In addition the formation of both episulfides and oxides from the vicinal diaxial thiocyanatohydrin acetates was discussed on the basis of the natures of the substituents.
