Total synthesis of (+/-)-11 alpha-hydroxyprogesterone by cyclization of a polyunsaturated epoxide.

The total synthesis of a typical 11-hydroxylated steroid, (+/-)-11 alpha-hydroxyprogesterone, was achieved by picric acid-catalyzed tricyclization of a polyunsaturated epoxide appropriately substituted with ketal, hydroxyl, and acetylenic units. This epoxide was prepared by a multistage sequence featuring two successive alkylations of intermediary, monocyclic sulfones. The first sulfone intermediate was obtained by means of a short sequence starting from levulinic acid and diethyl succinate and involving a selective cyclization reaction.

Hydrogenative deoxygenation of organic compounds: Direct conversion of amides to alkanes.

Through the use of (Cp(2)TiH)(x) or (Cp(2)Ti)(1-2), in which Cp is C(5)H(5) (cyclopentadienyl ligand), it is possible to effect not only the previously known direct reduction of aldehydes and esters to alkanes but also the one-step conversion to alkane of amides derived from selected primary aromatic amines.