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.

Immunoaffinity-Induced Signal Depression of Cu-MOF-74 for Label-Free Electrochemical Detection of Cardiac Troponin I

“…The broad peak in the range 3000–3650 cm –1 was assigned to the hydrogen bonds of the free hydroxyl groups. The strong bands at 1641 and 1423 cm –1 were assigned to the stretching vibration of the −COOH bond, which confirmed the presence of H 4 dhtp ligands in the framework. The bands at 698 cm –1 were related to the stretching and plane bending vibrations of the benzene ring.…”

A stable 3D Cd(ii) metal–organic framework for highly sensitive detection of Cu2+ions and nitroaromatic explosives

“…Metal-organic frameworks (MOFs) have diversity of structures, [7][8][9] which have been widely applied in recent years. [10][11][12][13][14][15][16][17] Among different types of MOFs, excellent stability and specic structure endow luminescent MOFs the ability to detect metal ions (Cu 2+ , Fe 3+ ), explosives (nitrobenzene, 4-nitrophenol, TNT, and 2,4,6-trinitrophenol), and inorganic anions (NO 3…”

Metal–organic framework (MOF)-, covalent-organic framework (COF)-, and porous-organic polymers (POP)-catalyzed selective C–H bond activation and functionalization reactions

“…For instance, the research teams of Phan and Truong reported the hydroacylation of terminal alkynes with glyoxalates using a Cu-MOF-74/base catalytic system at 100 °C for 4 h (Scheme 23). 84 Particularly, the performance of this MOF catalyst was found to be superior to that of the homogeneous copper salts and other MOFs (Ni-MOF-74, Zn-MOF-74, Fe 3 O(BDC) 3 , In(OH)(BDC), UiO-66, and a series of Cu-based MOFs). 84…”

“…84 Particularly, the performance of this MOF catalyst was found to be superior to that of the homogeneous copper salts and other MOFs (Ni-MOF-74, Zn-MOF-74, Fe 3 O(BDC) 3 , In(OH)(BDC), UiO-66, and a series of Cu-based MOFs). 84…”