A Charge-Enhanced Hydrogen Bonding Strategy for Halogen Bond Activation in Catalysis

Abstract Catalysis underpins modern chemical innovation, yet halogen-bond catalysts remain underdeveloped. Herein, we introduce a charged hydrogen bond-enhanced halogen bond (HBeXB) platform that intensifies σ-hole electrophilicity to unlock reactivity. Mechanistic, spectroscopic, and computational studies reveal a cooperative network of hydrogen bonding, halogen bonding, and nonclassical C–H interactions, delivering exceptional catalytic rates. The modular design of these scaffolds establishes a broadly applicable strategy for next generation organocatalysis.