The synthesis of negatively substituted epoxides, such as 3β-acetoxy-17β-bromo-16α, 17α-oxidoandrostane (I), and their reactions with amines are described. The resulting amino ketones (II) were identical with those obtained in a substitution reaction from the 16α-bromo 17-ketone IV with amines. Reduction of amino ketones II leads to the corresponding amino alcohols. 16β-Alkylamino 17-ketones (II) also resulted from the interaction of acetoxy epoxide VIII with amines. The opening of the three-membered ring is interpreted as a concerted process. The synthesis of 2-alkylamino-3-cholestanones cannot be effected via 2-bromo-3-cholestanone but was accomplished by ring opening of acetoxy epoxide IX with amines.