Synthesis of 5,10-seco analogs of testosterone.

A number of 5,10-seco analogs of testosterone has been synthesized starting from products of the radical oxidation of 3beta,17beta-diacetoxy-5alpha-androstan-5alpha-ol. The obtained compounds possess a flexible 10-membered ring with substituents (O, -OH) at C-3 and C-5. Similar derivatives with an (E)- and (Z)-Delta(1(10))-double bond have been prepared also.

A new type of steroids with a cyclobutane fragment in the AB-ring moiety.

The synthesis of a 5,10-seco steroid containing two double bonds in a AB-macrocycle as well as the preparation of a steroidal skeleton with a cyclobutane fragment is described. The structures of these compounds are different from those of natural steroids, but they are very similar with respect to conformation of the carbon skeleton.

Isolation and structure elucidation of new radical oxidation products of 5-hydroxy steroids.

Three new products have been isolated from the lead-tetraacetate version of the hypoiodite oxidation of 3beta,17beta-diacetoxy-5-hydroxy-5 alpha-androstane. Along with the expected 1(10)-unsaturated 5,10-seco steroidal 5-ketones, the fragmentation reaction gave two epimeric C-4 iodides. Their structural assignment was based on X-ray data of one of them ((4R,10S)-4-iodo-3beta,17beta-diacetoxy-5,10-secoandrostan-5-one).

Reaction of (13S)-13-iodo-6beta-methoxy-3alpha,5-cyclo-13,14-seco-5alpha-androstane-14,17-dione with hydroxylamine and its application to the synthesis of new 13,14-seco steroids.

The synthesis of 13,14-seco steroids starting from easily available (13S)-13-iodo-6beta-methoxy-3alpha,5-cyclo-13,14-seco-5alpha-androsta-14,17-dione is described. The C-17 ketone was converted regioselectively into its oxime with simultaneous stereoselective deiodination at C-13. The remaining C-14 carbonyl group was then reduced stereoselectively with Ca(BH4)2.