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

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 catalytically active for the synthesis of 1,2-dicarbonyl-3-enes than other MOFs including Cu-2(BDC)(2)(DABCO), Cu-3(BTC)(2), Cu(BDC), Cu-2(NDC)(2)(DABCO), Cu4I4(DABCO)(2), Ni-MOF-74, Zn-MOF-74, Fe3O(BDC)(3), In(OH)(BDC), and Zr6O4(OH)(4)(BDC)(6). 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.