Dual-Ligand System for Mild Decarbonylative Suzuki–Miyaura Cross-Coupling of Aroyl Chlorides

Cooperativity between a pair of phosphine ligands enables general Pd-catalyzed decarbonylative Suzuki–Miyaura cross-couplings between (hetero)aroyl chlorides and (hetero)arylboronic acids under mild conditions. Experimental and computational studies support a ligand-relay mechanism in which each phosphine preferentially promotes different elementary steps, enhancing the yield and selectivity relative to using either ligand alone. These results validate empirical, mechanism-agnostic screening through pooling–deconvolution as a means for identifying synthetically enabling catalytic methods and mechanisms for multiligand cooperativity.