Bridging chemistry and biology for light-driven new-to-nature enantioselective photoenzymatic catalysis.

Merging enzymes with light-driven photocatalysis has given rise to the burgeoning field of photoenzymatic catalysis. This approach combines the high reactivity from photoexcitation with the exceptional selectivity of biocatalysis, providing exciting opportunities to tackle challenges in enantioselective radical reactions and to access new-to-nature enzyme reactivities. This tutorial review aims to provide a comprehensive introduction to this interdisciplinary topic, catering to the growing interest from communities in asymmetric catalysis, photocatalysis, radical chemistry, enzyme engineering, and synthetic biology. We summarize the fundamental principles of utilizing light to power enzymatic reactions and different strategies exploring enantioselective photoenzymatic systems, including natural cofactor-based photoenzymatic catalysis, photocatalyst/enzyme synergistic catalysis, synthetic cofactor-based artificial photoenzymes, and cofactor-free photoenzymatic catalysis. We also discuss the challenges and prospects of enantioselective photoenzymatic catalysis in advancing sustainable asymmetric synthesis.