Recent advances in radical enabled selective C sp 3 -F bond activation of multifluorinated compounds.

Fluorine-containing molecules have found broad applications in pharmaceutical and agrochemical industries as introducing fluorine into a molecule could significantly tune the biological activities of parent molecules. Thus, the synthesis of fluorine-containing molecules has received substantial attention over the past few decades. As a complementary strategy for the synthesis of fluorinated compounds through new C sp 3 -F bonds formation, selective cleavage of inert C sp 3 -F bonds from easily-available and cost-effective multifluorinated molecules, such as fluoroalkylaromatics, α-trifluoromethyl alkenes and α-multifluorinated carbonyl compounds, has been emerging as an attractive alternative to access fluorine-containing molecules. Moreover, the inherent nature of radical reactions offers the opportunity for the selective C sp 3 -F functionalizations to occur under mild conditions. In this regard, the development of photoredox catalysis, transition-metal catalysis, or electrochemistry to enable radical species generation via selective C sp 3 -F cleavage has gained broad attention and substantial progress has been made over recent years. This highlight summerizes the recent advances in the single-electron-transfer enabled selective functionalizations of C sp 3 -F bonds in multifluorinated compounds via radical pathways.