Photoenzymatic Catalysis for Organic Synthesis

Photoenzymatic catalysis emerged as a powerful tool for generating reactive radical intermediates within tunable protein active sites. For decades, only two photoenzymes were known in nature; DNA photolyase and light-dependent protochlorophyllide reductase. While mechanistically interesting, these enzymes hold little synthetic value. However, over the past decade, natural and non-natural photoenzymes have been discovered and developed, catalyzing important reactions for synthetic organic chemists. These enzymes have been evolved to address selectivity challenges that small molecule catalysts struggle to solve. This chapter will review the development of photoenzymatic catalysts for application in chemical synthesis through November 2022. We will focus on general catalytic strategies, mechanistic details, and protein engineering strategies.