Novel reactions of perfluoroalkylphenyl sulfides with organolithium reagents

Article abstract of DOI:10.1016/0022-1139(94)03209-I

The reaction of anisole with organolithium reagents, commonly known as ortho-directed metallation, is of considerable synthetic utility in organic chemistry and as such has attracted considerable attention in recent years.Over the past 50 years, several mechanisms have been proposed to account for the observed regioselective metallation.For the first time, the reaction of perfluoroalkylphenyl sulfides with organolithium reagents has been investigated and found to furnish products resulting from the replacement of the perfluoroalkyl moieties with alkyl groups derived from the metallating agents.Phenyltrifluoromethyl ether, the anisole analog, failed to undergo metallation.A rationalization for the formation of unusual products via mediation of a single-electron-transfer process is presented in this paper together with the spectral data of the products. - Keywords: Reactions; Perfluoroalkylphenyl sulfides; Organolithium reagents; NMR spectroscopy; Mass spectrometry; Orthometallation