Deoxygenative C(sp3)-N(sp3) Cross-Coupling Enabled by Nickel Metallaphotoredox Catalysis.

Metallaphotoredox catalysis has emerged as a powerful platform for generating high-energy radicals from native functionalities. This approach integrates radical reactivity with transition metal catalysis to enable controlled bond formation. However, the synthesis of tertiary amines remains a significant challenge due to their redox sensitivity under photoredox conditions and the inherent difficulty of C(sp3)-N(sp3) reductive elimination. Herein, we describe a deoxygenative C-N cross-coupling between alcohols and N-hydroxylamine esters to form tertiary amines. Oxidation of the tertiary amine products is kinetically suppressed under optimized conditions, while a sterically demanding ancillary ligand promotes reductive elimination. This methodology displays broad substrate scope, accommodating diverse functional groups, heterocycles, and pharmaceutical derivatives.