Diaryliodonium Salts Enabled Arylation, Arylocyclization, and Aryl‐Migration

Abstract Our research interest focusing on synthetic methodology with diaryliodonium salts, is summarized in this account. Besides employing a dual activation strategy of C−I and ortho C−H bonds, we have introduced vicinal functional groups at ortho ‐positions of diaryliodonium salts, in which their unique reactivities have been explored in various processes, including arylation, diarylation, cascade annulation, benzocyclization, arylocyclization, and intramolecular aryl migration. The variety of mechanisms of these reactions that involves either transition metals, especially palladium in organometallic catalysis, or transition‐metal free conditions, were discussed in the context.