The application of abundant and inexpensive fluorine
feedstock
sources to synthesize fluorinated compounds is an appealing yet underexplored
strategy. Here, we report a photocatalytic radical hydrodifluoromethylation
of unactivated alkenes with an inexpensive industrial chemical, chlorodifluoromethane
(ClCF2H, Freon-22). This protocol is realized by merging
tertiary amine-ligated boryl radical-induced halogen atom transfer
(XAT) with organophotoredox catalysis under blue light irradiation.
A broad scope of readily accessible alkenes featuring a variety of
functional groups and drug and natural product moieties could be selectively
difluoromethylated with good efficiency in a metal-free manner. Combined
experimental and computational studies suggest that the key XAT process
of ClCF2H is both thermodynamically and kinetically favored
over the hydrogen atom transfer pathway owing to the formation of
a strong boron–chlorine (B–Cl) bond and the low-lying
antibonding orbital of the carbon–chlorine (C–Cl) bond.