Rearrangements in the Cerium(IV) and Manganese(III) Oxidations of Substituted Naphthalenes and the NIH Shift Mechanism

Article abstract of DOI:10.1016/S0040-4020(01)87034-4

Ceric ammonium sulphate oxidation of 1- and 1,4-disubstituted naphthalenes gives 2- and/or 2,3-disubstituted 1,4-naphthoquinones through migration of substituents (D, Br, Ph).Similar rearrangements are also observed in the manganese(III) oxidation and also in the anodic oxidation of these substrates.The results are consistent with the proposal that these oxidations go through the formation of radical cation followed by reaction with H2O and further oxidation of the radical to the carbocationic intermediate on the way to the corresponding 1,4-naphthoquinone.Oxidation of 1,4-diphenylnaphthalene gives 2,3-diphenyl-1,4-naphthoquinone or 4-hydroxy-2,4-diphenyl-1(4)H-naphthalenone.The results are in accordance with the conclusion that such rearrangements do not require prior formation of arene oxide intermediates, originally proposed for the NIH shift mechanism.