Journal of Organic Chemistry p. 3753 - 3762 (1984)
Update date:2022-07-29
Topics:
Suginome, Hiroshi
Yamada, Shinji
We set out to describe a two-step transformation of saturated hydroxy steroids into oxasteroids with an oxgen-containing ring of the same size as that of the starting ring.The irradiation of the hypoiodites generated in situ by means of the reaction of the hydroxy steroids with an excess of mercury(II)oxide and iodine gives novel formates arising from the successive reactions triggered by a β-scission of the corresponding alkoxy radical.These formates can readily be transformed into oxasteroids by a treatment with a complex metal hydride or methyllithium.The method is exemplified by the transformations of 1-, 3-, and 17-hydroxy steroids into the corresponding oxasteroids.Experiments in which we have used 18O labeled mercury(II)oxide as a source of I218O provide evidence that the oxygen atom in the oxasteroids is derived from the hydroxyl group of the starting alcohol and not from the oxygen of mercury(II)oxide.This suggests that the pathway of the formation of the formates involves (a) β-scission of the corresponding alkoxy radical to give a carbon centered radical intermediate with a carbonyl group, (b) its intramolecular combination with the carbonyl oxgen to form a tetrahydropyranyl radical or an oxepanyl radical, (c) its reaction with iodine oxide or *OI to generate a new hypoiodite, and (d) a regiospecific β-scission of the second alkoxy radical generated from it.
View MoreContact:0510-85393305
Address:1619 Huishan Avenue, Huishan District, Wuxi,
Contact:+86-535-8888888
Address:No.161 Haishi Rd.
KA-SHING Business Trade Macau Co., Ltd.
Contact:00853-28430045
Address:23rd Floor, Block 3 La Cite, Areia Preta, Macao
NINGBO PANGS CHEM INT’L CO.,LTD.
Contact:+86-574-27666845
Address:FLOOR 21,BUILDING NO.11,XIN TIAN DI,NO.689 SHI JI ROAD,NINGBO CHINA
Hefei EnliPharma Tecnology Co.,Ltd
Contact:0086-551-66399836
Address:Qing Cheng ShuiXiang Building 805, Mengcheng North Road , ShuangFeng Economic Development Zone Anhui HeFei
Doi:10.1007/s00706-016-1788-5
(2017)Doi:10.1002/adsc.200800536
(2009)Doi:10.1021/acs.inorgchem.0c02112
(2020)Doi:10.1016/j.bmcl.2009.04.098
(2009)Doi:10.1021/jo00264a001
(1989)Doi:10.1021/ja01500a034
(1960)