Difluoromethylphenoxathiiniumsalt:Anewgeneralandversatiledifluoromethylatingreagentwithdivergent·CF2H,CF2H+,and:CF2reactivities<iclass="icon-zqcb"></i>

Development of practical and versatile electrophilic difluoromethylating reagent is still a grand challenge so far due to its inherent instability or low reactivity.Herein,we report the design and synthesis of difluoromethyl phenoxathiinium tetrafluoroborate（PT-CF2H+BF4-） as a novel difluoromethylating reagent,which proves to be a bench-stable,general,powerful and versatile reagent with divergent·CF2H,CF2H+,and:CF2 reactivities.Making use of this reagent,we demonstrated a vast array of difluoromethyl radical transfer reactions via diverse pathways involving photocatalyst-free visible-light induction,visible-light photoredox catalysis and visible-light mediation single electron transfer of EDA complex.Moreover,the green and highly effective CF2H+ and:CF2 transfer reactions were also readily accomplished.