Novel estrones by oxidation of the benzylic positions of the estrane skeleton with tert-butyl hydroperoxide and cobalt acetate

Four new estrone derivatives were isolated after treatment of estrone 3-methyl ether (3-methoxyestra-1,3,5(10)-trien-17-one (3) with tert-butyl hydroperoxide and cobalt acetate. Three of the four steroidal compounds-the 9alpha-(tert-butylperoxy)-6-one 4, the 9alpha-hydroxy-6-one 5, and the 9beta-hydroxy-6-one 7-originated from oxidation at the 6- and 9-positions. In contrast, oxidation of 3 to a 9beta-(tert-butylperoxy) compound afforded the 8-hydroxy-9-cyclodecanone derivative 6 through a molecular rearrangement involving the cleavage of the 8-9 bond. The structures of the compounds were secured by spectroscopic evidence including COSY, HSQC, and NOESY experiments combined with X-ray crystallographic analysis and molecular modeling studies. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).