Cu-α-diimine Compounds Encapsulated in Porous Materials as Catalysts for Electrophilic Amination of Aromatic C–H Bonds

Electrophilic amination has emerged as a more environmentally benign approach to construct arene C–N bonds. However, heterogeneous catalysts remain largely unexplored in this area, even though their use could facilitate product purification and catalyst recovery. Here we investigate strategies to heterogenize a Cu(2,2′-bipyridine) catalyst for the amination of arenes lacking a directing group with hydroxylamine-O-sulfonic acid (HOSA). Besides immobilization of Cu on a metal–organic framework (MOF) or covalent organic framework (COF) with embedded 2,2′-bipyridines, a ship-in-a-bottle approach was followed in which the Cu complex is encapsulated in the pores of a zeolite. Recyclability and hot centrifugation tests show that zeolite Beta-entrapped CuII(2,2′-bipyridine) is superior in terms of stability. With N-methylmorpholine as a weakly coordinating, weak base, simple arenes, such as mesitylene, could be aminated with yields up to 59%, corresponding to a catalyst TON of 24. The zeolite could be used in three consecutive runs without a decrease in activity. Characterization of the catalyst by EPR and XAS showed that the active catalytic complex consisted of a site-isolated CuII species with one 2,2′-bipyridine ligand.