However, the application of these synthetic intermediates has been limited due to the laborious and hazardous preparation process. In comparison to the above synthetic approaches, the direct radical fluorosulfonamidation process for synthesizing sulfamoyl fluorides utilizing fluorosulfonamide radicals has received minimal attention. Sulfuryl fluoride (SO2F2) is an abundant inflammable industrial raw material that has been mainly used as an electrophilic "FSO2+" synthons in previous studies . Up until 2022, Wang (our prior research) and Liao independently demonstrated the activation of sulfuryl fluoride by an imidazole scaffold to produce benzimidazolium fluorosulfonate reagents, successfully executing the radical fluorosulfonylation process . Nevertheless, inadequate activation patterns prevent further applications of sulfuryl fluoride. Based on our previous work, we initially envisioned whether we could develop a new activation method for sulfuryl fluoride to generate fluorosulfonamide radicals (Figure ). However, the generation of fluorosulfonamide radical (• NSO2F) from inert SO2F2 gas has met with inevitable difficulties due to the relatively small magnetic/quadrupole moments, the high homolytic bond dissociation energy of the S(VI)-F bond (BDE = 90.5 ± 4.3 kcal/mol) and suitable novel activation skeleton for activating sulfuryl fluoride (Figure ). Thus, the development of single electron transfer (SET) process of SO2F2 for radical fluorosulfonamidation represents great challenges and in high demand.