Synergistic catalysis of Cu+/Cu0 for efficient and selective N-methylation of nitroarenes with para-formaldehyde

In this paper, an inexpensive heterogeneous copper nanoparticles catalyst derived from CuAl-layered double hydroxide via an in situ topotactic transformation process was developed. Cu nanoparticles with uniform size were homogeneously dispersed on amorphous Al2O3 with strong metal-support interaction. Characterization results reveals that the Cu-0 and Cu+ were simultaneously formed with Cu+ species as the dominant sites on the surface during the reduction process. The resultant catalyst Cu/Al2O3 demonstrates high catalytic activity, selectivity and durability for the reductive N-methylation of easily available nitroarenes in a cost-efficient, environmentally friendly and cascade manner. A broad spectrum of nitroarenes could be efficiently N-methylated to their corresponding N,N-dimethyl amines with good compatibility of various functional groups. The protocol is also applicable for the late-stage functionalization of biologically and pharmaceutically active nitro molecules. A structure-function relationship discloses that Cu-0 and Cu+ sites on the surface pronouncedly boosts the reaction efficiency in a synergistic manner, in which Cu-0 could facilitate H-2 production and N-methylation of anilines, while Cu+ is considerably more active and participates in the overall process of the selective N-methylation of nitroarenes. Moreover, the catalyst also showed a strong stability and could be easily separated for successive reuses without an appreciable loss in activity and selectivity. (C) 2019 Elsevier Inc. All rights reserved.