Regioselective Radical Hydroboration of gem-Difluoroalkenes: Synthesis of α-Borylated Organofluorines.

A regioselective radical hydroboration of gem-difluoroalkenes was developed for the synthesis of α-difluoroalkylborons. The reaction features excellent regioselectivity, broad substrate scope, and good functional group capability. DFT calculations implicated the remarkable α-selectivity was driven from the kinetically and thermodynamically more favorable α-addition step. The resulting α-difluoroalkylborons could be readily converted into NHC-borane-tethered monofluoroalkenes, which demonstrated unique reactivity and applicability in the synthesis of monofluoroalkene derivatives through transformations of the boron unit.