We herein describe a rational design of a heterogeneous catalyst composed of a dinuclear cuprate anion being immobilized electrostatically on one surface of Janus-type nanosheets while the other surface is decorated with highly hydrophobic octyl groups. The catalyst was found to be well dispersible in the organic phase of a biphasic aqueous/organic mixture. It was characterized by means of elemental analysis, atomic absorption spectroscopy, mass spectrometry, N2 absorption-desorption analysis, thermogravimetric analysis, scanning electron microscopy (SEM), and solid-state 13C and 29Si cross-polarization magic-angle spinning nuclear magnetic resonance spectroscopy. The Janus nature of the catalyst was investigated by employing a selective surface labeling method and by means of SEM. The catalyst shows higher activity compared to a non-Janus analogue in a biphasic synthesis. It was successfully used for the azide-alkyne cycloaddition and the Chan-Lam C-N coupling reaction. In addition, new and simple ways have been established for the production of a coumarin-triazole derivative and for the synthesis of the biologically active compound Monastrol via a solvent-free Biginelli reaction. The role of the dinuclear copper centers is discussed mechanistically.
Keywords: C−N bond formation; Huisgen cycloaddition; Janus interphase catalyst; dinuclear copper; interfacial catalysis.