Catalytic dynamic kinetic reductive addition of simple aldehydes and aldimines with heterobiaryl triflates: harnessing both central and axial chirality.

A nickel-catalyzed intramolecular dynamic kinetic resolution (DKR) strategy has been developed for the enantioselective synthesis of axially chiral heterobiaryls from racemic azabiaryl triflates. Using a reductive addition mechanism, this method controls both axial and central chirality, offering broad substrate scope, excellent enantioselectivity, and atroposelectivity. The resulting chiral heterobiaryls were effectively employed as organocatalysts and chiral ligands in asymmetric transformations, highlighting their synthetic utility. Mechanistic studies indicate a synergy between kinetic resolution and nickel-mediated stereochemical inversion, addressing challenges in concurrent axial and stereochemical control.