Synthesis of difluoromethylated benzylborons via rhodium(I)-catalyzed fluorine-retainable hydroboration of gem-difluoroalkenes

A rhodium-catalyzed hydroboration of aryl gem-difluoroalkenes leads to a regioselective construction of a series of α-difluoromethylated benzylborons. The use of cationic rhodium catalyst and a biphosphine ligand with large bite angle was crucial for reactivity by offering good regioselectivity and diminishing the undesired β-F elimination. [Display omitted] The synthesis of borylated organofluorines is of great interest due to their potential values as synthons in modular construction of fluorine-containing molecules. Reported herein is a rhodium-catalyzed hydroboration of aryl gem-difluoroalkenes leading to a series of α-difluoromethylated benzylborons. The use of cationic rhodium catalyst and a biphosphine ligand with large bite angle was crucial for reactivity by offering good regioselectivity and diminishing the undesired β-F elimination. Preliminary derivatizations of the products were conducted to showcase the utility of this protocol.