Nickel-Catalyzed Enantioselective Reductive Arylation and Heteroarylation of Aldimines via an Elementary 1,4-Addition

Nickel catalysts of chiral pyrox ligands promoted enantioselective reductive arylation and heteroarylation of aldimines, using directly (hetero)aryl halides and sulfonates. The catalytic arylation can also be conducted with crude aldimines generated from condensation of aldehydes and azaaryl amines. Mechanistically, density functional theory (DFT) calculations and experiments pointed to an elementary step of 1,4-addition of aryl nickel(I) complexes to N-azaaryl aldimines.

Automated summary

Nickel catalysts with chiral pyrox ligands were used for enantioselective reductive arylation and heteroarylation of aldimines using (hetero)aryl halides and sulfonates. Crude aldimines generated from the condensation of aldehydes and azaaryl amines can also be used for catalytic arylation. The mechanism involves an elementary step of 1,4-addition of aryl nickel(I) complexes to N-azaaryl aldimines, as supported by density functional theory (DFT) calculations and experiments.