Sulfonium Ylide Enabled, Copper-Catalyzed Difluoromethylation, Monofluoromethylation, and Monofluoroalkylation of Lithium Aryl nButyl Borates

A copper-catalyzed fluoroalkylation of lithium aryl nbutyl borates with electrophilic fluoroalkylating reagent YlideFluor for the preparation of di-, trifluoromethyl-, and monofluoroalkyl-substituted (hetero)arenes under mild conditions was described. Control experiments indicated that a fluoroalkyl radical, rather than a difluorocarbene intermediate, is involved in the catalytic process. In addition, stoichiometric reactions demonstrated that transmetalation of copper catalyst with lithium aryl nbutyl borate takes place before the single-electron-transfer (SET) oxidation of an ate-type Cu(I) intermediate [CuI(Ar)(SCN)]− by YlideFluor. Based on these mechanistic results, a reasonable catalytic cycle for the copper-catalyzed fluoroalkylation of lithium aryl nbutyl borates was proposed.