Three groups of (5 alpha,13 alpha)-D-azasteroids, (5 alpha,13 alpha)-3-hydroxy-17a-aza-D-homoandrostans (12), (5 alpha,13 alpha)-3-hydroxy-17-aza-D-homoandrostans (15), and (5 alpha,13 alpha)-3-hydroxy-17-azaandrostans (17), were designed and synthesized as key precursors for the further preparation of a new family of potential GABAA receptor modulators from commercially available natural steroids (5 alpha)-3-hydroxyandrostane-17-ones (7).