Nickel-Catalyzed Amination of Alkyl Electrophiles

Bimolecular nucleophilic substitution S(N)2is the earliestand most important means of amination of alkyl electrophiles; itspractical utilization is largely limited to primary or activated substrates.Furthermore, a persistent challenge lies in establishing C(sp(3))-N bonds from alkyl substrates in cross-coupling chemistryusing palladium and nickel catalysts. Therefore, the methods of constructingC(sp(3))-N bonds remain rare from alkyl electrophiles.The existing routes are limited to copper catalysis and photoredoxcatalysis. Here, we demonstrate an alternative amination strategyfor rapid construction of C(sp(3))-N bonds from accessiblealkyl electrophiles, which were used as radical precursors under nickelcatalysis by Ni (III) species reductive eliminations in high efficiency.

Automated summary

Bimolecular nucleophilic substitution S(N)2 is the earliest and most important means of amination of alkyl electrophiles, but its practical utilization is mostly limited to primary or activated substrates. Establishing C(sp(3))-N bonds from alkyl substrates in cross-coupling chemistry using palladium and nickel catalysts has been a persistent challenge. The existing routes are restricted to copper catalysis and photoredox catalysis. In this study, we demonstrate an alternative amination strategy that rapidly constructs C(sp(3))-N bonds from accessible alkyl electrophiles by utilizing Nickel (III) species reductive eliminations under high efficiency catalysis.