Synthesis and Reactivity of Iodepinium Salts

Seven‐membered cyclic diaryliodonium salts, known as iodepinium salts, remain a significantly underexplored class of hypervalent iodine compounds. This scarcity is primarily attributed to the lack of efficient synthetic methodologies. Herein, we report an effective protocol for the synthesis of iodepinium triflates via the oxidative cyclization of iodinated ( Z )‐stilbenes. In addition to establishing a substrate scope of 10 derivatives with yields up to 83%, the structural features of the unique seven‐membered ring were elucidated via X‐ray crystallography. Furthermore, initial investigations into their reactivity reveal unique decomposition and transformation pathways.