Halogen Atom Transfer-Induced Homolysis of C–F Bonds by the Excited-State Boryl Radical

A novel reactivity toward C–F bond functionalization has been developed, which could be designated as fluorine atom transfer (FAT). A photoexcited state of an N-heterocyclic carbene-ligated boryl radical exhibits a transcendent reactivity, capable of activating chemically inert carbon–fluorine bonds through homolysis. Combined experimental and computational studies suggest that the ligated boryl radical species directly abstracts a fluorine atom from the organofluoride substrates to provide valuable carbon-centered radicals.