Role of base in palladium-catalyzed arylation of carbanions

The arylation reaction of carbanions, derived from certain sulfones, cyanoacetic ester and malononitrile, with aryl bromides (using the catalytic system of Pd₂dba₃/3L, L=PPh₃, PtBu₃) as well as the reaction of the carbanions with one equivalent of 4-CF₃C₆H₄ Pd(PPh₃)₂Br has been studied. These reactions proceed smoothly provided that the base stronger than the initial carbanion is present in the reaction mixture. In the absence of the above type of base the reactions do not proceed at all. Taking that into account we have proposed a novel mechanism of palladium-catalyzed arylation of CH-acids. The main feature of this mechanism is the accelaration of the reductive elimination due to the deprotonation of the intermediate ArPdL₂CHXY. The correlation between the carbanion reactivity and the pK_a values for related CH-acids as well as the ligand effect are discussed in the framework of the proposed mechanism.