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 Cu 2 (BDC) 2 (DABCO), Cu 3 (BTC) 2 , Cu(BDC), Cu 2 (NDC) 2 (DABCO), Cu 4 I 4 (DABCO) 2 , Ni‐MOF‐74, Zn‐MOF‐74, Fe 3 O(BDC) 3 , In(OH)(BDC), and Zr 6 O 4 (OH) 4 (BDC) 6 . Cu/MOF‐74 also exhibited better performance than other homogeneous copper catalysts, including Cu(OAc) 2 , Cu(NO 3 ) 2 , CuI, CuBr, CuCl, CuCl 2 , and CuBr 2 . 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.