Triazolium NHCs with Polyfluoroalkoxy Phenyl Substitutes: Synthesis and Preliminary Application as Organocatalyst

Abstract The N-substituents are essential for the performance of N-heterocyclic carbene (NHC) organocatalyst. Introducing polyfluoroalkoxy groups into the N-substituents of triazolium NHCs resulted in a unique fluorine effect. Calculations of Natural Bond Orbital charge distributions and dihedral angles validate the unique impact of the polyfluoroalkoxy groups on the electronic structure and conformation of the NHCs. Notably, this modification strategy led to remarkably enhanced enantioselectivities in various NHC-catalyzed reactions, including radical trifluoroacylation, photocatalyzed radical coupling, and electro-catalyzed dynamic kinetic resolution.