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 (<b>dcypfu</b>) ligand. The nickel(II) (<b>1</b>), palladium(II) (<b>2</b>), and platinum(II) (<b>3</b>) 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 <b>1</b> and <b>2</b> 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 <b>dcypt</b>-supported systems. In contrast, nickel (pre)catalysts supported by either the <b>dcypfu</b> or the <b>dcypt</b> ligand displayed similar performances (and limitations) toward the intramolecular decarbonylative synthesis of ethers. Both complexes <b>1</b> and <b>2</b> 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/K₃PO₄ system delivered consistently high yields regardless of substrate electronics. These results identify complex <b>2</b> as a powerful and general (pre)catalyst for decarbonylative thioether synthesis and highlight the potential of newly reported <b>dcypfu</b> as a versatile supporting ligand for group 10 metal catalysis.