Oxidative Addition of Aryl Tosylates to Palladium(0) and Coupling of Unactivated Aryl Tosylates at Room Temperature

Aryl tosylates are attractive substrates for Pd-catalyzed cross-coupling reactions, but they are much less reactive than the more commonly used aryl triflates. We report the oxidative addition of aryl tosylates to Pd(PPF-t-Bu)[P(o-tolyl)3] and to Pd(CyPF-t-Bu)[P(o-tolyl)3] at room temperature to produce the corresponding palladium(II) aryl tosylate complexes. In the presence of added bromide ions, arylpalladium(II) bromide complexes were formed. The rate of oxidative addition was accelerated by addition of either coordinating or weakly coordinating anions, and the reactions were faster in more polar solvents. The mild conditions for oxidative addition allowed for the development of Pd-catalyzed Kumada couplings and amination reactions of unactivated aryl tosylates at room temperature. The catalysts for these mild couplings of aryl tosylates were generated from palladium precursors and the sterically hindered Josiphos-type ligands that induced oxidative addition of aryl tosylates to Pd(0) at room temperature.