4- and 6-azasteroids have been shown to be potent inhibitors of human 5α-reductase and certain azasteroids have shown significant clinical benefit in the treatment of androgen-related disorders. In an effort to expand the diversity of steroidal heterocycles synthetically accessible for structure-activity relationship exploration, a novel reaction sequence was applied to the preparation of the 6-azasteroid framework. To this end, photolysis of the oxaziridine derived from 17β-carbomethoxy-3β-triisopropylsilyloxy-6-azaandrost-5-ene (1) yielded a novel 7, 5-steroidal ring system that was evaluated for inhibition of human type 1 and 2 5α-reductase.