Bis(pyrimidine)-based palladium catalysts: synthesis, X-ray structure and applications in Heck–, Suzuki–, Sonogashira–Hagihara couplings and amination reactions

The synthesis of N,N-bis(pyrimid-2-yl)amine (1), N-acetyl-N,N-bis(pyrimid-2-yl)amide (2), N-norborn-2-ene-5-ylbis(pyrimid-2-yl)carbamide (4) is described. The Pd-complex N-acetyl-N,N-bis(pyrimid-2-yl)amine palladium dichloride (3) has been prepared from compound 2 and its X-ray structure has been determined. A polymer supported catalytic system (6) was prepared via ring-opening metathesis copolymerization of 4 with 1,4,4a,5,8,8a-hexahydro-1,4,5,8-exo-endo-dimethanonaphthalene (HDMN-6) and subsequent loading with PdCl2. Both the homogeneous and heterogeneous catalysts 3 and 6 were active in Heck–, Suzuki–, Sonogashira–Hagihara-type couplings and amination reactions using aryl iodides, bromides and chlorides.