Ppm‐Level Oxazoline‐Fused Acenaphthoimidazolylidene Palladium Catalyst: Efficient Indirect Activation of Primary Amide C–N Bonds for Suzuki–Miyaura Cross‐Coupling

Herein, we report the efficient Suzuki–Miyaura cross‐coupling reactions of N ‐acylglutarimides—directly derived from primary amides—with arylboronic acids, catalyzed by an oxazoline‐fused acenaphthoimidazolylidene palladium catalyst, thus enabling the indirect and highly efficient activation of primary amides. At ppm‐level loading (0.05 mol%, 500 ppm), the catalyst afforded 99% yield of aryl ketones in 5 h, with a TON of 34,800 and TOF of 2650 h −1 , outperforming reported NHC‐Pd systems. It features broad substrate scope, compatible with arylboronic acids (EDGs, EWGs, polycyclic, alkenyl, and heterocyclic) and N‐acylglutarimides from aromatic, heteroaromatic, and aliphatic primary amides. Notably, it achieved 93% yield in 5 h for the green synthesis of a flumorph key intermediate using THF as solvent.