Emerging Strategies for Asymmetric Synthesis: Combining Enzyme Promiscuity and Photo‐/Electro‐redox Catalysis

Abstract As an emerging opportunity to expand the reactivity repertoire of enzymes to achieve unnatural transformations of enzymes in organic synthesis, enzyme promiscuity has attracted great interest in recent years. The combination of enzyme catalysis and photo‐/electro‐redox catalysis which can benefit from both the exquisite selectivity of enzymes and unique chemical transformations accessible to photo‐/electro‐chemistry has many advantages, such as new reactivity, high enantioselectivity, green synthesis, and high yields. In the past decades, most photoenzymatic catalysis and enzymatic electrosynthesis mainly focused on exploiting regenerated cofactors to function in native enzymatic activity. However, recent developments have demonstrated that combining enzyme promiscuity and photo‐/electro‐redox catalysis can unlock new asymmetric reactions. This minireview highlights these emerging strategies and covers the literature from 2016 to date. Furthermore, the future development direction of this field is prospected.