Iodine Catalysis for C(sp3)–H Fluorination with a Nucleophilic Fluorine Source

Abstract

AbstractIodine catalysis was developed for aliphatic fluorination through light‐promoted homolytic C−H bond cleavage. The intermediary formation of amidyl radicals enables selective C−H functionalization via carbon‐centered radicals. For the subsequent C−F bond formation, previous methods have typically been limited by a requirement for electrophilic fluorine reagents. We here demonstrate that the intermediary instalment of a carbon–iodine bond sets the stage for an umpolung, thereby establishing an unprecedented nucleophilic fluorination pathway.