[2,2′-Bipyridin]-6(1H)-one, a Truly Cooperating Ligand in the Palladium-Mediated C–H Activation Step: Experimental Evidence in the Direct C-3 Arylation of Pyridine

Abstract

The ligand [2,2′-bipyridin]-6(1H)-one (bipy-6-OH) has a strong accelerating effect on the Pd- catalyzed direct arylation of pyridine or arenes. The isolation of relevant intermediates and the study of their decomposition unequivocally show that the deprotonated coordinated ligand acts as a base and assists the cleavage of the C−H bond. Mechanistic work indicates that the direct arylation of pyridine with this ligand occurs through a Pd(0)/Pd(II) cycle. Because of this dual ligand− intramolecular base role, there is no need for an available coordination site on the metal for an external base, a difficulty encountered when chelating ligands are used in coupling reactions that involve a C−H cleavage step.