Synthesis and applications of a new palladacycle as a high active catalyst in the Suzuki couplings

The reaction of biphenyl-based phosphine P(o-C6H4Me)Ph-2 (1) with Pd(OAc)(2) in toluene affords the air and water stable palladacycle (2) as a binuclear compound which has been characterized by multinuclear NMR spectroscopy and elemental analysis as a mixture of cis and trans isomers with relative intensity of 1:3, respectively. This palladacycle is a highly efficient catalyst precursor for the coupling of aryl boronic acids and aryl halides. Both activated and deactivated aryl bromides and chlorides are efficiently coupled in the presence of 2 to furnish the corresponding cross-coupled products in excellent yields, and a wide variety of functional groups are tolerated in aryl halides. This methodology has also been extended for the coupling of bromoarylphosphines and bromoarylphosphine oxides with aryl boronic acids for the generation of hindered corresponding products. (C) 2008 Elsevier B.V. All rights reserved.