Copper-Catalyzed Functionalization of Benzylic C-H Bonds with N -Fluorobenzenesulfonimide: Switch from C-N to C-F Bond Formation Promoted by a Redox Buffer and Brønsted Base.

A copper catalyst in combination with N-fluorobenzenesulfonimide (NFSI) has been reported to functionalize benzylic C-H bonds to the corresponding benzylic sulfonimides via C-N coupling. Here, we reported a closely related Cu-catalyzed method with NFSI that instead leads to C-F coupling. This switch in selectivity arises from changes to the reaction conditions (Cu/ligand ratio, temperature, addition of base) and further benefits from inclusion of MeB(OH)(2) in the reaction. MeB(OH)(2) is shown to serve as a "redox buffer" in the reaction, responsible for rescuing inactive Cu(II) for continued promotion of fluorination reactivity.