Demethyl oxidative halogenation of diacyl dimethylsulfonium methylides.

α-Halo-α-methylthio-β-ketosulfones containing a quaternary halocarbon stereocenter were prepared via selective demethyl oxidative halogenations of diacyl dimethylsulfonium methylides in moderate to excellent yields (39 examples; up to 98%). The current protocols directly and efficiently introduce a halogen atom into organic compounds with high functional group tolerance under metal-free conditions.