Bimolecular nucleophilic substitution SN2 is the earliest and most important means of amination of alkyl electrophiles; its practical utilization is largely limited to primary or activated substrates. Furthermore, a persistent challenge lies in establishing C(sp3)-N bonds from alkyl substrates in cross-coupling chemistry using palladium and nickel catalysts. Therefore, the methods of constructing C(sp3)-N bonds remain rare from alkyl electrophiles. The existing routes are limited to copper catalysis and photoredox catalysis. Here, we demonstrate an alternative amination strategy for rapid construction of C(sp3)-N bonds from accessible alkyl electrophiles, which were used as radical precursors under nickel catalysis by Ni (III) species reductive eliminations in high efficiency.