Dynamic Kinetic Reductive Grignard-Type Addition for the Construction of Axial and Central Chirality

This study describes a photoredox/cobalt dual-catalyzed asymmetric Grignard-type addition reaction, enabling the synthesis of axially chiral hexatomic (six–six) N-heterobiaryls bearing the extra chiral secondary alcohol unit via an efficient dynamic kinetic asymmetric transformation of racemic N-heterobiaryl triflate substrates. The conversion facilitated via both photoredox and classical reductive reaction conditions exhibits good functional group tolerance, a broad substrate scope, and satisfactory stereoselectivity. Furthermore, control experiments and density functional theory calculations provide preliminary mechanistic insights.