Thiamine diphosphate-dependent enzymes: mechanistic principles, stereoselective C–C bond formation, and synthetic biocatalytic applications

-selective. These enzymes hold significant promise for biotechnological applications, particularly through protein engineering to tailor catalytic activity and stereoselectivity. Moreover, ThDP-dependent enzymes have been implicated in the pathogenesis of Alzheimer's disease, diabetes, and tumor proliferation. This review also summarizes relevant clinical applications and the use of competitive inhibitors. By integrating modular architectures, cofactor synergy mechanisms, regulatory networks, and emerging frontiers in photoelectrochemical biocatalysis, this review highlights the broad potential of ThDP-dependent enzymes in both fundamental research and translational applications.