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Herein, a copper metal–organic framework, termed as VNU-18, containing penta-coordinated sites was successfully synthesized and fully characterized. This material was demonstrated to be an efficient heterogeneous catalyst for the oxidative C–H activation viaN–H bonds. The optimized conditions are applicable for the synthesis of pharmaceuticals constructed by α-amino carbonyl skeletons.

We have described an efficient method for oxidative cross coupling reactions between activated N–H amines and terminal alkynes using heterogeneous Cu2(BDC)2(BPY) as recyclable catalyst (BDC = benzene-1,4-dicarboxylate; BPY = 4,4′-bipyridine). The optimal conditions involved the use of inexpensive NaHCO3base and oxygen as terminal oxidant in toluene solvent at 80 °C. Reactions proceeds efficiently, and high selectivity with only trace amount of diynes as well as good yields were achieved in a short reaction time. The Cu2(BDC)2(BPY) exhibited excellent catalytic activity and selectivity as compared to other Cu-MOFs on a broad reaction scope. Interestingly, the presence of bipyridine ligand was shown to enhance the catalyst stability. Thus, the Cu2(BDC)2(BPY) could be facilely separated from the reaction mixture by simple centrifugation and could be reused several times with only a slight decrease in catalytic activity.