Journal of the Chemical Society. Perkin transactions II p. 815 - 824 (1989)
Update date:2022-08-03
Topics:
Beckwith, Athelstan L. J.
Davies, Alwyn G.
Davison, Ian G. E.
Maccoll, Allan
Mruzek, Margaret H.
The rearrangement of 5α-hydroperoxy-3β-hydroxycholest-6-ene in solution under 18O2, gives isotopically normal 7α-hydroperoxy-3β-hydroxycholest-5-ene, whereas the epimerization of this product to give 7β-hydroperoxy-3β-hydroxycholest-5-ene involves incorporation of 73-83% of 18O2 into the hydroperoxy group. These two reactions proceed through the corresponding hydroperoxyl radicals, which have different e.s.r. spectra and which therefore must exist as separate and distinct species. The former reaction shows a first-order dependence on hydroperoxide concentration, and a half-order dependence on t-butyl hyponitrite which was added as an initiator. It is suggested that the first reaction involves a sigmatropic [2,3]-rearrangement, whereas the second reaction proceeds through a dissociative mechanism.
View MoreContact:+44 7958 511245
Address:PO Box 469, Manchester, UK
Contact:0086-22-23410962
Address:17-201, Ningfuli, Shuishanggongyuandong road,Nankai district, Tianjin, China
website:http://www.mingchem.com/en/index
Contact:0519-85170101-802
Address:Fifth Floor,B of Beihua Buliding,520 Road of Science and Education City,Changwu middle road NO.801,Wujin District,Changzhou,Jiangsu province
Contact:18698110882
Address:1303 No2 building,LuoMa Garden,YongAn Road,Hexi District,Tianjin city
Contact:86-21-34622192，13917187091，21-34622765
Address:No. 500 Caobao Road Shanghai P.R China
Doi:10.1246/cl.1988.1589
(1988)Doi:10.1021/jo902164z
(2010)Doi:10.1021/ic9018053
(2010)Doi:10.1002/hlca.200900087
(2009)Doi:10.1002/anie.201902779
(2019)Doi:10.1016/j.bmc.2011.04.041
(2011)
