Expanding the chemical space of biosynthesis through chemistry-inspired enzymatic transformations

This review highlights recent advances in chemistry-inspired enzymatic catalysis, particularly focusing on transformations enabled by heme, flavin, nicotinamide, thiamine diphosphate, and pyridoxal phosphate-dependent enzymes. We discuss how principles of organic chemistry have been applied to expand enzymatic reactivity beyond native biological functions, enabling various transformations not found in nature. In addition, recent studies have demonstrated the integration of these reactions into metabolic pathways, allowing the production of molecules beyond the scope of natural metabolism. Together, these developments illustrate how chemistry-inspired enzymatic transformations can expand the chemical space accessible through biosynthesis.