Palladium Immobilized onto Functionalized Magnetic Nanoparticles as Robust Catalysts for Amination and Room‐Temperature Ullmann Homocoupling of Aryl Halides: A Walk Around the C−F Bond Activation

Abstract The first example of a heterogeneous catalytically active system for Buchwald–Hartwig and Ullmann homocoupling of unactivated aryl halides (fluorobenzene) is presented. The novel magnetic heterogeneous palladium catalyst was synthesized by immobilization of palladium ions onto an aminopyridine‐functionalized Fe 3 O 4 . The catalyst was fully characterized by FTIR spectroscopy, temperature‐programmed reduction, thermogravimetric analysis, CHN elemental analysis, transmission electron microscopy, field‐emission scanning electron microscopy, X‐ray diffraction, energy‐dispersive X‐ray spectroscopy, and atomic absorption spectroscopy. By using this catalyst system, various types of primary and secondary amines reacted with different types of aryl halides, even fluorobenzene. This catalyst can also efficiently transform all types of haloarenes into biaryl derivatives by Ullmann reaction at room temperature. Therefore, it is a promising catalyst in the area of C−F bond activation. The catalyst was reused several times and no significant loss of activity was observed.