Abstract Upon desulfurization with Raney Ni, the condensed heterocycles 2a, b prepared by cyclization from β-ketosulfoxides 1a, b gave β-ketones 3a, b, which were condensed with 2- carbethoxymethyl-piperidine 4 to afford the 10, 17-diazasteroid 6 and the 10-aza-17- thiasteroid 7, respectively.