The functionalization of saturated hydrocarbons. Part 25. Ionic substitution reactions in GoAggIV chemistry: The formation of carbon-halogen bonds

Article abstract of DOI:10.1016/S0040-4020(01)80735-3

GoAgg^IV chemistry (Fe (III) species, tert-butyl hydroperoxide in a mixture of pyridine and acetic acid) in the presence of LiCl can transform saturated hydrocarbons efficiently into the corresponding alkyl chlorides. The transformation into monosubstituted alkyl derivatives by "ionic trapping" reagents arising from the interception of the first intermediate of the system supports the presence of a high valent ^VFe-C species. Mechanistic studies suggest a possible pathway operating via an Fe-centered ligand coupling. In addition, the production of alkyl chlorides and alkyl bromides could also be achieved employing this system in the presence of halogenating reagents such as CCl₄ and BrCCl₃.