Abstract
5α,6α-Iminocholestan-3β-ol (IV) and its 3α-hydroxy-isomer (V) have been prepared and their structures established. Their reactions with sodium azide in acetone–water (2 : 1) produce the corresponding trans-diaxial amino-azides. The ratio of the reaction rates is ca. 1 : 2, respectively. The mechanisms of the reactions of the steroidal aziridines are discussed and comparison is made between these compounds and the related epoxides.

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