Progesterone enone

The synthesis of ( )-D-homotestosterone and ( )-progesterone has been accomplished via a now classical procedure involving the use of an isoxazole as an annelating agent (67JA5464). The enolate (424), prepared from 10-methyl-A1,9-octalin-2,5-dione, was alkylated by the 4-chloromethylisoxazole (425). The octalindione (426) was treated sequentially with one equivalent of sodium borohydride, hydrogenated, hydrogenolyzed and refluxed with sodium methoxide and then with sodium hydroxide to afford the crystalline enone (427). 

The use of silica gel surfaces to modify photoprocesses continues to be of interest. The present report deals with photoaddition of alkenes to the steroidal enone (44).It is presumed that, in the adsorbed state on silica gel, the steroid will present the normally hindered side, i.e., the g-face is attacked by the alkene and the a-face is adsorbed on to the gel. The photoadditions were compared with those carried out in methanol. Thus with allene the two photoproducts (45) and (46) were obtained in 90 and 10% yields, respectively, at -78 °C in methanol, while on silica gel, both at -78 °C and at ambient temperature, the same two products were obtained in 46 and 53% yield. Similar results were obtained using ethene and cyclopentene. The photocycloaddition of ethyne and propyne to progesterone and testosterone in solution yields the cycloadducts (47) and (48), with a preference for the former mode of addition being observed. These results are in conflict with those of de Mayo and co-workers. ... 

Also analyzed androsterone (UV 210), cortexolone, cortisone, estradiol (UV 280), estrone (TJV 280), ethinyl estradiol (UV 280), ethisterone, hydrocortisone, hydroig progesterone, lynestrenol (UV 210), medroxyprogesterone acetate, medroxyprogesterone, methandi-enone, methylandrostenediol (UV 210), methylprednisolone acetate, methylprednisolone, methyltestosterone, nandrolone, norethisterone, prednisolone acetate, prednisolone, pregnenolone (UV 210), progesterone, testosterone... 

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