Synergistic Photoenzymatic Catalysis Enables Enantioselective Synthesis of γ-Amides via a Ternary Electron Donor–Acceptor Complex

The development of photoenzymatic non-natural reactions facilitates the synthesis of challenging high-value-added chiral compounds. However, this approach typically requires enzyme engineering to enhance both the catalytic activity and selectivity. Herein, we report a synergistic photoenymatic system comprising wild-type GluER and exogenous Ru(bpy)₃Cl₂·6H₂O that enables the photoenzymatic enantioselective hydroalkylation of olefins. In this system, Ru(bpy)₃Cl₂·6H₂O replaces protein engineering, driving an efficient catalytic cycle. The radical initiation was by electron transfer between excited Ru(bpy)₃Cl₂·6H₂O and an in situ-formed ternary electron donor-acceptor (EDA) complex. This synergistic photo/biocatalytic system decreases the time-consuming and labor-intensive nature while providing an environmentally friendly methodology for chemical synthesis.