NOVEL REACTIONS OF PERFLUOROALKYLPHENYL SULFIDES WITH ORGANOLITHIUM REAGENTS

The reaction of anisole with organolithium reagents, commonly known as ortho-directed metallation, is of considerable synthetic utility in o rganic chemistry and as such has attracted considerable attention in r ecent years. Over the past 50 years, several mechanisms have been prop osed to account for the observed regioselective metallation. For the f irst time, the reaction of perfluoroalkylphenyl sulfides with organoli thium reagents has been investigated and found to furnish products res ulting from the replacement of the perfluoroalkyl moieties with alkyl groups derived from the metallating agents. Phenyltrifluoromethyl ethe r, the anisole analog, failed to undergo metallation. A rationalizatio n for the formation of unusual products via mediation of a single-elec tron-transfer process is presented in this paper together with the spe ctral data of the products.