Iodine‐Mediated Regioselective 2,3‐Difunctionalization of Indoles: A Cascade C−H Arylsulfenylation and Ether Cleavage Strategy

We report an iodine‐mediated, oxidative 2,3‐difunctionalization of indoles utilizing disulfides and electron‐rich trimethoxybenzene derivatives under mild conditions. This metal‐free protocol enables the one‐pot assembly of C2‐aryl‐C3‐sulfenylindoles with excellent regioselectivity. Notably, the reaction features a unique cascade involving the selective cleavage of a specific methoxy group, offering a regioselective approach to complex indole–phenol hybrids. Mechanistic studies indicate a radical pathway and a sequential C3‐sulfenylation/C2‐arylation process. The method demonstrates broad functional group tolerance and scalability, offering a sustainable route to polysubstituted indoles.