Inter- and Intramolecular Coupling Reactions Catalyzed by Group 10 Metal Complexes of the 3,4-Bis(dicyclohexylphosphino)furan (dcypfu) Ligand

We report the synthesis, characterization, and catalytic evaluation of group 10 metal complexes supported by the new 3,4-bis(dicyclohexylphosphino)furan ( dcypfu ) ligand. The nickel(II) ( 1 ), palladium(II) ( 2 ), and platinum(II) ( 3 ) dichloride complexes were prepared in high yields and fully characterized by multinuclear NMR spectroscopy, mass spectrometry, and X-ray diffraction studies. The catalytic performances of complexes 1 and 2 were examined toward two representative C–C and C–S bond-forming reactions. These complexes showed moderate to good activity in the Suzuki–Miyaura cross-coupling of aryl bromides with aryl boronic acids under green conditions but remained less effective than the analogous dcypt -supported systems. In contrast, nickel (pre)catalysts supported by either the dcypfu or the dcypt ligand displayed similar performances (and limitations) toward the intramolecular decarbonylative synthesis of ethers. Both complexes 1 and 2 exhibited excellent reactivity in the intramolecular decarbonylative coupling of aryl thioesters. The Ni II /Zn system proved competent across a broad substrate range but was sensitive to electronic effects, whereas the Pd II /K 3 PO 4 system delivered consistently high yields regardless of substrate electronics. These results identify complex 2 as a powerful and general (pre)catalyst for decarbonylative thioether synthesis and highlight the potential of newly reported dcypfu as a versatile supporting ligand for group 10 metal catalysis.