4,5-Secoandrostanes by Eschenmoser's reaction

Abstract

17β-Benzoyloxy-4,5-secoandrost-3-yn-5-one (V), accessible from testosterone in three steps, can be converted both to Δ5-unsaturated alkynes of the type XXV (via axial hydroxy derivative XVII) and to alkynes of the type XXVI (by hydrogenolysis of equatorial methanesulfonate XXIII). These compounds were hydrated and hydrolysed to 17β-hydroxy-4,5-secoandrost-5-en-3-one and 17β-hydroxy-4,5-secoandrostan-3-one (XXX and I respectively). Catalytic hydrogenation of compound XXX with tritium afforded [5,6-3H2]-derivative XXXI.