Enzymatic Promiscuity for Organic Synthesis and Cascade Process

Enzymatic promiscuity, namely the possibility that one active site of an enzyme can catalyze several different chemical transformations, has been an important research field and valuable synthesis tool for protein engineering and synthetic chemistry. This review will focus on promiscuous enzyme-mediated reactions that are useful in organic synthesis. Examples include promiscuous hydrolysis reactions, Michael addition, Markovnikov addition, aldol condensation, Henry reaction, Mannich reaction, Epoxidation reaction, Baeyer-Villiger oxidation, radical polymerization and tandem reactions catalyzed by natural enzymes or engineered enzymes with existing or induced catalytic promiscuity. Among these examples, many enzymes from different family have been verified to be able to catalyze the same type of reaction through distinct mechanism. Many complex compounds or important intermediates can be synthesized using promiscuous enzymes or through novel synthesis pathways. These examples support the enormous potential of enzymatic promiscuity in synthetic chemistry.