A mixed NCP pincer palladacycle as catalyst precursor for the coupling of aryl halides with aryl boronic acids

The reaction of phosphinite Me2NCH2C C(CH2)(2)OP(i-Pr)(2) (2) with Li2PdCl4 in methanol at room temperature affords the air and water stable mixed pincer palladacycle (Me2NCH2(Cl)C=C(CH2)(2)OP(i-Pr)(2)-kappa N kappa C kappa P)PdCl (3) whose structure has been ascertained by means of an X-ray diffraction study. This pincer palladacycle is a highly efficient catalyst precursor for the coupling of aryl boronic acids and aryl chlorides. Both electron-rich and -poor aryl chlorides are efficiently coupled in the presence of 3 to furnish the corresponding cross-coupled products in excellent yields, and a wide variety of functional groups are tolerated in both aryl chloride and aryl boronic acid. The experimental protocol has also been extended for the coupling of iodo and bromo arenes with aryl boronic acids for the generation of hindered biphenyls. The coupling process afforded very good yields of biphenyl products containing two ortho substituents. Steric hindrance is more sensitive for ortho substituents in the aryl boronic acid and is more pronounced when the coupling reaction involves three ortho substituents. (c) 2005 Elsevier B.V. All rights reserved.