Reductant‐Free Enantioselective <i>Aza</i> ‐Reformatsky Reaction Enabled by Synergistic Visible Light Photocatalysis and Lewis Acid Catalysis

Abstract Classical aza ‐Reformatsky reaction generally involves excess reductants. Herein, we developed a visible light‐induced catalytic asymmetric aza ‐Reformatsky reaction via a chiral Lewis acid‐assisted direct excitation of imines without additional reductants, enabling the carbon–iodine bond cleavage of iododifluoromethyl ketones and the subsequent enantioselective radical coupling. This protocol provided an ingenious access to chiral β ‐amino ketones containing a gem ‐difluorine moiety. The mechanistic studies including radical trapping experiment, NMR experiment, electron paramagnetic resonance experiment, cyclic voltammetry experiment and spectroscopic analysis rationalized the reaction process.