Yukichi Kishida

Steroid Series: Part XIV Synthesis of 6-Aza- and 7-Aza-5β-steroidsPart XV Synthesis of 6-Aza- and 7-Aza-5α-steroids

3β-Acetoxy-B-nor-5β-cholestan-6-one (Ia) afforded only one isolatable oxime (IIa), while oximation of 3β, 17β-diacetoxy-B-nor-5β-androstan-6-one (Ib) yielded two isomeric oximes (IIb and IIIb). 7-Aza-5β-cholestan-3β-ol (VIa), 7-aza-5β-androstane-3β, 17β-diol (VIc), and 6-aza-5β-androstane-3β, 17β-diol (VIIc) were synthesized by Beckmann rearrangement of these oximes, followed by reduction with lithium aluminium hydride. The structure of the aza-steroids were established by conversion of the intermediate lactams (IVa, b) into the lactones (IXa, b), prepared from the 3β-acetoxy-B-nor-6-oxo-5β-steroids (Ia, b) by Baeyer Villiger reaction.