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

Abstract

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.