On catalytic hydrogenation of Delta(9)-steroids (e.g. 3beta-hydroxy-5-methyl-19-nor-5beta-androst-9-en-17-one), four isomers were formed: 9alpha,10alpha-, 9alpha,10beta-, 9beta,10alpha- and 9beta,10beta-adducts. The product distribution was affected by the nature of the C-3 substituent. A chair conformation of A, B, and C rings was found in all of the products with the exception of the 9alpha,10alpha-adduct whose B ring adopts a twist boat conformation. The products were utilized for the synthesis of dihydrotestosterone analogues.