Synthesis of 1,2-Dicarbonyl-3-enes by Hydroacylation of 1-Alkynes with Glyoxal Derivatives Using Metal–Organic Framework Cu/MOF-74 as Heterogeneous Catalyst

Abstract

A crystalline copper-based metal-organic framework Cu/MOF-74 was synthesized, and used as an efficient heterogeneous catalyst for the synthesis of 1,2-dicarbonyl-3-enes by means of the hydroacylation of 1-alkynes with glyoxal derivatives in the presence of a base. Cu/MOF-74 was found to be more catalyti-cally active for the synthesis of 1,2-dicarbonyl-3-enes than other MOFs including Cu₂(BDC)₂(DABCO), Cu₃(BTC)₂, Cu(BDC), Cu₂(NDC)₂(DABCO), Cu₄I₄(DABCO)₂, Ni-MOF-74, Zn-MOF-74, Fe₃O(BDC)₃, In(OH)(BDC), and Zr₆O₄(OH)₄(BDQ₆. Cu/MOF-74 also exhibited better performance than other homogeneous copper catalysts, including Cu(OAc)₂, Cu(NO3)₂, CuI, CuBr, CuCl, CuCl₂, and CuBr₂. The Cu/MOF catalyst was able to be recovered and reused several times without a significant degradation in catalytic activity. To the best of our knowledge, the formation of 1,2-dicarbonyl-3-enes has not previously been carried out under heterogeneous catalysis conditions.