Radical reactions enabled by polyfluoroaryl fragments: photocatalysis and beyond

Polyfluoroarenes have been known for a long time, but they are most often used as fluorinated building blocks for the synthesis of aromatic compounds. At the same time, due to peculiar fluorine effect, they have unique properties that provide applications in various fields ranging from synthesis to materials science. This review summarizes advances in the radical chemistry of polyfluoroarenes, which have become possible mainly with the advent of photocatalysis. Transformations of the fluorinated ring via the C-F bond activation, as well as use of fluoroaryl fragments as activating groups and hydrogen atom transfer agents are discussed. The ability of fluoroarenes to serve as catalysts is also considred. The review summarizes advances in the radical chemistry of polyfluorinated arenes under photocatalytic conditions. The fluoroaryl fragment serves as enabling motif for the reaction design and efficient generation of reactive intermediates.