Unlocking the Chain‐Walking Process in Gold Catalysis

The successful realization of gold‐catalyzed chain‐walking reactions, facilitated by ligand‐enabled Au(I)/Au(III) redox catalysis, has been reported for the first time. This breakthrough has led to the development of gold‐catalyzed annulation reaction of alkenes with iodoarenes by leveraging the interplay of chain‐walking and π‐activation reactivity mode. The reaction mechanism has been elucidated through comprehensive experimental and computational studies. A gold‐catalyzed chain‐walking process is presented herein by employing a ligand‐enabled Au(I)/Au(III) redox catalysis. This process is harnessed to develop a novel gold‐catalyzed annulation reaction of alkenes with iodoarenes by leveraging the interplay of chain‐walking and π‐activation reactivity mode.