Synthesis of (5α)-17-azaandrostan-3-ols and (5α)-17-aza-D-homoandrostan-3-ols and their N-acylated derivatives

Abstract Two groups of N -acylated D-azasteroids ( 4 and 5 ) were synthesized to explore structure-activity relationships for steroid modulation of GABA A receptor function. The target compounds were prepared conveniently from (5α)-3-hydroxyandrostan-17-ones ( 6 and 7 ) via the intermediate (5α)-17-aza-D-homoandrostan-3-ols ( 14 and 15 ) or (5α)-17-azaandrostan-3-ols ( 18 and 19 ) precursors in high overall yields. A Beckmann rearrangement and a Hofmann rearrangement were employed as two key steps in the synthetic sequences.