Syntheses of 2α- and 2β-deuterio-testosterones and -androst-4-ene-3,17-diones

Abstract

Testosterone and androst-4-ene-3,17-dione with a deuterium label in the 2α- or 2β-position have been synthesized from a common intermediate, 5α-androst-2-ene-5α,17β-diol. An improved preparation of the latter is described, together with its conversion via epoxidation, reductive epoxide opening, and subsequent oxidation and dehydration to 2β-labelled Δ⁴-3-oxo steroids. Treatment of the same precursor with labelled diborane leads, by a similar synthetic sequence, to both 2α- and 2β-labelled Δ⁴-3-oxo steroids. The stereochemical integrity of the products has been determined by high-field deuterium n.m.r.