Derivatives of 5α-androstan-3α- and 3β-ol with acrylonitrile side chain

Abstract

Aldehydes II - III were reacted with diethyl cyanomethylphosphonate and sodium hydride in 1,2-dimethoxyethane to give the respective pairs of unsaturated nitriles IVa and Va, VIa and VIIa, and VIIIa and IXa differing in configuration at the 20(21)-double bond. The pure isomers were obtained by chromatography on alumina, and the configuration at the double bond in them has been established on the basis of the coupling constants J(20, 21) in their 1H NMR spectra. Nitriles IVa - VIIa and IXa were converted via the corresponding hydroxy derivatives into hemisuccinates IVd - VIId and IXd, and into β-D-glucosides IVe - VIIe and IXe.