Photoexcited Enzymes for Asymmetric Csp3−Csp3 Cross‐Electrophile Couplings

Abstract Enzymes have several advantages over conventional catalysts for organic synthesis. Over the last two decades, much effort has been made to further extend the scope of biocatalytic reactions available to synthetic chemists, particularly by expanding the repertoire of enzymes for abiological transformations. In this regard, exciting new developments in the area of photobiocatalysis enable now the introduction of non‐natural reactivity in enzymes to solve long‐standing synthetic challenges. A recently described example from the Hyster group demonstrates in an unprecedented way how the combination of photochemistry with enzyme catalysis empowers the catalytic asymmetric construction of Csp3−Csp3 bonds with high chemo‐ and enantioselectivity.