Thiopseudourea ligated palladium complexes: synthesis, characterization and application as catalysts for Suzuki–Miyaura, Sonogashira, Heck and Hiyama reactions

Abstract

A series of new non-phosphine 1-(2-picolyl)-3-benzoylsubstituted-2-benzyl-2-thiopseudourea ligands 2a–2f have been synthesized in two steps from commercially available benzoyl chlorides. Treatment of these ligands with Pd(OAc)2 in a 1 : 1 molar ratio in dichloromethane (DCM) at room temperature provided convenient access to the corresponding N,N,O-tridentate palladium(II) complexes [Pd(OAc){ArCONHC(N(CH2Py)}SCH2C6H5] (Ar = C6H5 (3a); 4-F-C6H4 (3b); 4-Br-C6H4 (3c); 4-I-C6H4 (3d); 4-Me-C6H4 (3e); 3,4,5-(OMe)3-C6H2 (3f)) in almost quantitative yields. The new ligands and their palladium complexes were characterized by NMR, IR, ESIMS, and HRMS analysis. The molecular structure of complex 3c has been determined by X-ray single-crystal diffraction. These Pd(II) complexes have been used as catalysts for the Suzuki–Miyaura, Sonogashira, Heck and Hiyama cross-coupling reactions.