Abstract
Visible light activates "ene"-reductase to catalyze the cross-coupling reaction between aromatic compounds and diethyl bromomalonate. In this transformation, NADPH and its regeneration system are abandoned, and the cofactor FMN(ox) is employed to directly initiate the reaction. This reaction exhibits excellent substrate compatibility, with a maximum catalytic yield of 95%. It expands the range of radical precursors for "ene"-reductase-catalyzed reactions and diversifies the reaction types.