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 catalytically 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(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.