Recent advances in repurposing natural enzymes for new-to-nature asymmetric photobiotransformations

Photobiocatalysis, which integrates the strengths of visible-light-catalysis and enzymatic catalysis, has established itself as a pivotal tool for asymmetric synthesis. Over the past decade, several naturally occurring enzymes have been repurposed to catalyze diverse unnatural transformations that are notoriously difficult to realize using traditional methods. This emerging review focuses on the advancements in photobiocatalysis published from 2022 to December 2024 and also highlights earlier seminal reports related to the first demonstration. We organize this review by the coupling modes of visible-light and enzymes, including net-reduction photoenzymatic catalysis (typically) through the illumination of enzymatic electron donor–acceptor complexes, redox-neutral photoenzymatic catalysis via direct-visible-light excitation of enzymes, and synergistic dual photo-/enzymatic catalysis. With each section, the discussion is categorized by the type of enzyme, emphasizing the underlying mechanistic aspects, evolutionary trajectories and representative substrate scopes. We anticipate that this review will inspire further developments and application of photobiocatalysis.