Collect. Czech. Chem. Commun. 1985, 50, 1402-1414

4,5-Secoandrostanes by Eschenmoser's reaction

Alexander Kasala, Ladislav Kohouta and Jiří Filipb

a Institute of Organic Chemistry and Biochemistry, Czechoslovak Academy of Sciences, 166 10 Prague 6
b Institute for the Research, Production and Utilization of Radioisotopes, 102 27 Prague 10


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.