Ir(III)‐Catalyzed Selective ortho‐Monoiodination of Benzoic Acids with Unbiased C−H Bonds

An iridium‐catalyzed selective ortho‐monoiodination of benzoic acids with two equivalent C−H bonds is presented. A wide range of electron‐rich and electron‐poor substrates undergo the reaction under mild conditions, with >20:1 mono/di selectivity. Importantly, the C−H iodination occurs selectively ortho to the carboxylic acid moiety in substrates bearing competing coordinating directing groups. The reaction is performed at room temperature and no inert atmosphere or exclusion of moisture is required. Mechanistic investigations revealed a substrate‐dependent reversible C−H activation/protodemetalation step, a substrate‐dependent turnover‐limiting step, and the crucial role of the Ag(I) additive in the deactivation of the iodination product towards further reaction.