Mechanism of F+ Salts Catalyzed Aziridine Synthesis: F-Halogen Bonding Catalysis or F-Cation Transfer Catalysis?
Hao-Dong Tan , Liu Cai , Sean P. Bew , Xiao-Song Xue
Chinese Journal of Chemistry ›› 2025, Vol. 43 ›› Issue (24) : 3515 -3521.
Whether the fluorine atom (F) can engage in a halogen bond (XB) has remained a subject of ongoing debate. The discovery of N-fluoropyridinium triflate as a unique "F-cation organocatalyst" for aziridine synthesis has generally been considered the first instance of F-halogen bonding catalysis. Nevertheless, the mechanistic details of this reaction have remained elusive, and compelling evidence supporting the F-halogen bond catalysis has been lacking. In this study, we present an in-depth computational investigation of the mechanism of this reaction to gain insights into the intriguing role of the F-cation organocatalyst. Our results, however, are inconsistent with the previous prevalent F-halogen bonding catalysis mechanism but instead, bring to light a new fluorine cation transfer mechanism. This novel mechanism is supported by control experiments and can explain the observed cis-trans selectivity.
Halogen bond / Reaction mechanism / DFT calculation / Halogen cation transfer catalysis / Single-electron transfer
2025 SIOC, CAS, Shanghai, & WILEY-VCH GmbH
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