Iridium(III) Catalysts with an Amide‐Pendant Cyclopentadienyl Ligand: Double Aromatic Homologation Reactions of Benzamides by Fourfold C−H Activation

The synthesis, characterization, and catalytic performance of iridium(III) catalysts that bear an amide‐pendant cyclopentadienyl ligand ([Cp^AIrI₂]₂) is reported. These [Cp^AIrI₂]₂ catalysts were obtained from the complexation of a Cp^A ligand precursor with [Ir(cod)OAc]₂ followed by oxidation. Double aromatic homologation reactions of benzamides with alkynes by fourfold C?H activation proceeded in good to high yield with these [Cp^AIrI₂]₂ catalysts, demonstrating their superior catalytic performance in this challenging transformation.