Reported is an achiral Cp Rh /chiral carboxylic acid catalyzed asymmetric C-H alkylation of diarylmethanamines with a diazomalonate, followed by cyclization and decarboxylation to afford 1,4-dihydroisoquinolin-3(2H)-one. Secondary alkylamines as well as nonprotected primary alkylamines underwent the transformation with high enantioselectivities (up to 98.5:1.5 e.r.) by using a newly developed chiral carboxylic acid as the sole source of chirality to achieve enantioselective C-H cleavage by a concerted metalation-deprotonation mechanism.

The synthesis, characterization, and catalytic performance of iridium(III) catalysts that bear an amide‐pendant cyclopentadienyl ligand ([CpAIrI2]2) is reported. These [CpAIrI2]2 catalysts were obtained from the complexation of a CpA 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 [CpAIrI2]2 catalysts, demonstrating their superior catalytic performance in this challenging transformation.

Reported is an achiral CpxRhIII/chiral carboxylic acid catalyzed asymmetric C−H alkylation of diarylmethanamines with a diazomalonate, followed by cyclization and decarboxylation to afford 1,4‐dihydroisoquinolin‐3(2H)‐one. Secondary alkylamines as well as nonprotected primary alkylamines underwent the transformation with high enantioselectivities (up to 98.5:1.5 e.r.) by using a newly developed chiral carboxylic acid as the sole source of chirality to achieve enantioselective C−H cleavage by a concerted metalation‐deprotonation mechanism.

The synthesis, characterization, and catalytic performance of an iridium(III) catalyst with an electron‐deficient cyclopentadienyl ligand ([CpEIrI2]2) are reported. The [CpEIrI2]2 catalyst was synthesized by complexation of a precursor of the CpE ligand with [Ir(cod)OAc]2, followed by oxidation, desilylation, and removal of the COD ligand. The electron‐deficient [CpEIrI2]2 catalyst enabled C−H amidation reactions assisted by a weakly coordinating ether directing group. Experimental mechanistic studies and DFT calculations suggested that the high catalytic performance of [CpEIrI2]2 is due to its electron‐deficient nature, which accelerates both C−H activation and IrV‐nitrenoid formation.

The synthesis, characterization, and catalytic performance of iridium(III) catalysts that bear an amide‐pendant cyclopentadienyl ligand ([CpAIrI2]2) is reported. These [CpAIrI2]2 catalysts were obtained from the complexation of a CpA 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 [CpAIrI2]2 catalysts, demonstrating their superior catalytic performance in this challenging transformation.