Photoenzymatic new-to-nature transformations via electron donor-acceptor complexes

Recent advances have demonstrated that certain enzymes utilizing photoactive cofactors can be redirected upon light excitation to catalyze reactions entirely unrelated to their evolved functions. Given that charge-transfer interactions between substrates and cofactors can be facilitated by the spatial proximity afforded by enzyme active sites, electron donor-acceptor (EDA) complexes have emerged as a powerful strategy for asymmetric synthesis in photoenzymatic radical processes. This review primarily summarizes recent progress in the development of EDA complex-mediated abiological transformations in photoenzymatic reactions, highlighting their capacity to enable the asymmetric construction of diverse molecular skeletons.