Electron Donor‐Acceptor Complexes in Perfluoroalkylation Reactions

Electron‐donor‐acceptor complexes (EDA) can be established through halogen‐bonding interactions between the N lone electron pair from organic bases (or N‐/O‐centered anions) and perfluoroalkyl iodides RF–I. These EDA complexes can be activated thermally or photochemically, and will be shown to be responsible for new C–RF bond formation reactions, bypassing the use of visible‐light photocatalysts (either organic or organometallic) or harsh reaction conditions, thus simplifying reaction protocols, work‐up and analysis. Through this strategy, diverse reaction types can be realized, such as atom transfer radical additions, homolytic aromatic substitutions, and multicomponent reactions.