Non-Noble-Metal Metal–Organic-Framework-Catalyzed Carboxylative Cyclization of Propargylic Amines with Atmospheric Carbon Dioxide under Ambient Conditions

Abstract

The coupling reaction of propargylic amines and carbon dioxide (CO 2 ) to synthesize 2-oxazolidinones is an important reaction in industrial production, and yet harsh reaction conditions and noble-metal catalysts are often required to achieve high product yields. Herein, one novel noble-metal-free threedimensional framework, [Mg 3 Cu 2 I 2 (IN) 4 (HCOO) 2 (DEF) 4 ] n (1), assembled by magnesium and copper clusters was synthesized and applied to this reaction. Compound 1 displays excellent solvent stability. Importantly, 1, acting as heterogeneous catalyst, can highly catalyze the cyclization of propargylic amines with CO 2 under atmospheric pressure at room temperature, which can be recycled at least five times without an obvious decrease of the catalytic activity. NMR spectroscopy, coupled with 13 C-isotope-and deuterium-labeling experiments, clearly clarifies the mechanism of this catalytic system: CO 2 was successfully captured and converted to the product of 2-oxazolidinones, the CC bond of propargylic amines can be effectively activated by 1, and proton transfer was involved in the reaction process. Density functional theory calculations are further conducted to uncover the reaction path and the crucial role of compound 1 during the reaction.

Soft Metal–Organic Frameworks Based on {Na@Ln6} as a Secondary Building Unit Featuring a Magnetocaloric Effect and Fluorescent Sensing for Cyclohexane and Fe3+

“…Metal–organic frameworks (MOFs) containing two-dimensional and three-dimensional porous coordination polymers have been rapidly developed in the past two decades, − not only because of their rich and fascinating topological structures, − but also because of their various potential applications in nonlinear optics, , biomedicine, − sensors, , catalysis, − gas adsorption and separation, etc. − As a large branch of the MOF family, lanthanide metal–organic frameworks (Ln-MOFs) exhibit special and interesting topologies due to the high coordination numbers and flexible coordination modes of the Ln 3+ ions. − Compared with transition MOFs, − Ln-MOFs have unique magnetic properties and sensitive luminescence properties based on the special 4f electronic configuration of Ln 3+ ions. − …”

Self-Assembly Bifunctional Tetranuclear Ln2Ni2 Clusters: Magnetic Behaviors and Highly Efficient Conversion of CO2 under Mild Conditions

“…The problems presented by the anthropogenic emission amount of CO 2 , which has been the main cause of ocean acidification and global warming, are becoming a major priority with the increasing public awareness of environmental matters. , At the same time, nontoxic, abundant, and renewable CO 2 is indeed an ideal C1 resource. In this regard, it is indispensable to investigate CO 2 capture and sequestration to reduce the amount of carbon dioxide by consumption. − As a result, numerous efforts have been focused on chemical conversion and selective adsorption and storage. − One of the most effective methods is converting CO 2 into value-added chemical feedstocks. − The cycloaddition of CO 2 and epoxides to cyclic carbonates has been widely studied for two reasons: (1) high reactivity and green chemistry for 100% atom efficiency and (2) as important chemical intermediates of pharmaceuticals and specialty fine chemicals; the desired products of cyclic carbonates can be used in wide applications. − The thermodynamic stability and the kinetic inertness of CO 2 puts forward higher requirements for catalysts. However, many reported catalysts such as ionic liquids, , metal oxides, alkali metal salts, and functional polymers , still show some limitations, such as low catalytic reactivity, the use of additional solvents, dissatisfactory recyclability, even large CO 2 pressure, and high reaction temperature. − Therefore, it is pressing to develop new catalytic systems with high efficiency for CO 2 conversion.…”

Highly Efficient Conversion of Aziridines and CO2 Catalyzed by Microporous [Cu12] Nanocages

“…In the past few decades, MOFs as a new class of porous materials have displayed excellent catalytic performance due to their high porosity, highly dispersed catalytic active sites, large surface areas, and excellent reusability. epoxides, 22−26 propargylic alcohols, 27,28 propargylic amines, 29,30 terminal alkynes, 31,32 and so on). But comparably, only a limited number of MOFs can effectively catalyze the conversion of CO 2 with aziridines.…”