Reductive activation of PdII-precatalysts via decarboxylation of pivalate in direct C–H arylation reactions

Abstract

The mechanism of the reductive activation of Pd^II pre-catalysts has been extensively studied, but remains poorly understood. Herein, a combined computational and experimental approach is employed to clearly identify a Pd^II reduction process that has not been considered thus far. Pivalate, assumed to be a general base, was found to decarboxylate and act as a reductant, suggesting an alternative explanation for the superior performance of pivalic acid as an additive in Pd-catalyzed direct C–H arylation reactions.