Some 14β-cyanoandrostane derivatives

Abstract

A route to some 14β-cyanoandrostane derivatives is described which involves hydrocyanation of Δ¹⁴-16-ketones with the triethylaluminium–hydrogen cyanide complex, and the inertness of the 14-cyano-substituent towards acid hydrolysis and lithium aluminium hydride is established. On the other hand base hydrolysis leads to the formation of a ring D diosphenol having the 14β-H-configuration. An unusual dehydrobromination of a 15-bromo-androstane with lithium chloride is also discussed.