A practical method for C(sp3)-B bond activation was developed. Using a combination of alkyl trifluoroborates and N-iodosuccinimide (NIS), various C(sp3)-heteroatom bonds were readily generated in an efficient manner. Mechanistic studies revealed the bifunctional ability of NIS: mediating the formation of reactive halogenated intermediates and activating them via halogen bonding. This electrophilic activation of the reaction center enables the utilization of general heteroatom nucleophiles, which are used in a limited capacity in traditional 1,2-metalate rearrangements.