Selective bromination of γ-methylene C(sp3)−H bonds of aliphatic amides and δ-methylene C(sp3)−H bonds of nosyl-protected alkyl amines are developed using NBS as the brominating reagent and catalytic amount of CuII/phenanthroline complexes as the catalyst. Aryl and benzylic C−H bonds at other locations remain intact during this directed radical abstraction reaction.