Visible‐Light‐Induced Radical Cyclization of Unactivated Olefins with Perfluoroalkyl Iodides to Access Perfluoroalkylated <i>Ortho</i>‐Diazaheterocyclic Compounds

An efficient visible‐light‐driven strategy for the radical perfluoroalkylation/tandem cyclization of unactivated alkenes with perfluoroalkyl iodides (IR f ) has been developed, enabling efficient synthesis of perfluoroalkylated heterocyclic derivatives, including pyrazoles, pyridazines, and benzodiazepines. This methodology features broad substrate compatibility with 34 examples, affording the desired products in yields up to 81%. Results of mechanistic studies indicate that the formation of electron donor–acceptor complex between perfluoroalkyl iodides and TMEDA greatly initiates the reaction, avoiding the use of extra catalysts and oxidants.