Sequential one-pot <i>N</i> -alkylation and aminocarbonylation of primary amines catalyzed by heterobimetallic Ir/Pd complexes

The paper introduces bimetallic Ir/Pd complexes as catalysts to initiate an <i>N</i>-methylation coupled with an aminocarbonylation in a one-pot approach, in order to advance the field of carboxyamide synthesis. The iridium center initiates the reaction by selectively facilitating the <i>N</i>-methylation through amination, while the palladium center, in a complementary role, drives the carbonylation step. This bimetallic synergy not only streamlines the reaction sequence but also surpasses the efficiency and selectivity of monometallic Ir or Pd catalysts. Mechanistic studies suggest the presence of catalytically active hydride species within the <i>N</i>-methylation cycle, which were characterized experimentally and <i>via</i> quantum chemical calculations. The developed synthetic routes offer a sustainable, cost-effective, scalable and also unprecedented preparation method, with the bimetallic catalysts being robust and versatile.