Synthesis of oxido-bridged analogs of 18-hydroxyprogesterone.

18-Hydroxy-6,19-oxidoprogesterone and 18-hydroxy-11, 19-oxidoprogesterone were synthesized from readily available materials. The functionalization of C-18 was accomplished with phenyliodosodiacetate/iodine, whereas that of C-19 was carried out with the mercuric oxide/iodine system, both under irradiation with visible light. For 18-hydroxy-11,19-oxidoprogesterone, C-19 was functionalized before C-18, whereas the reverse order had to be used for the 6,19-oxido derivative.