Tetrahedron p. 1843 - 1846 (1980)
Update date:2022-08-03
Topics:
Schenk, C.
de Boer, Th. J.
Reaction of Grignard reagents and organolithium compounds (RM) with the congested 1-chloro-1-nitroso-2,2,6,6-tetramethylcyclohexane 1 leads to the formation of significant amounts of the reduction product 2,2,6,6-tetramethylcyclohexanone oxime 3 (61-90percent) together with the corresponding oxime O-R ether 4 (0-11percent).Attack on nitrogen is unimportant as shown by very low yields of nitrone.Formation of the products is rationalised with a pathway involving transfer of an electron from RM to 1.This leads-after separation of MCl-to a radical pair consisting of R. and the relatively stable iminoxy radical 2 (Schemes 1 and 2).Combination of these radicals explains formation of oxime ether 4 and nitrone 5, while reaction of iminoxy radical 2 with excess of RM can give oxime 3.Reactive radicals R. (i.e.Me,Ph, and to a minor extent n-Bu) are furthermore capable of abstracting hydrogen from the solvent (diethyl ether, toluene, or cumene), and the solvent derived radicals can also combine with 2 on oxygen, under formation of oxime ether (26percent of 6a).The corresponding benzyl- and cumyl ethers 6b and 6c are only formed in trace amounts because dimerisation of benzyl radicals (7percent) and cumyl radicals (22percent) is favoured.
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Doi:10.1002/jhet.5570450516
(2008)Doi:10.1246/cl.1980.869
(1980)Doi:10.1080/10426500490468119
(2004)Doi:10.1016/j.tet.2009.10.098
(2010)Doi:10.1039/c29710000542
(1971)Doi:10.1039/c7ra09995a
(2017)