Deaminative Borylation of Aliphatic Amines Enabled by Visible Light Excitation of an Electron‐Donor‐Acceptor Complex

: A deaminative strategy for the borylation of aliphatic primary amines is described. Alkyl radicals derived from the single-electron reduction of redox-active pyridinium salts, which can be isolated or generated in situ, were borylated in a visible light-mediated reaction with bis(catecholato)diboron. No catalyst or further additives were required. The key electron donor-acceptor complex was characterized in detail by both experimental and computational investigations. The synthetic potential of this mild protocol was demonstrated through the late-stage functionalization of natural products and drug molecules.