Green Catalytic Process for Cyclic Carbonate Synthesis from Carbon Dioxide under Mild Conditions

Abstract

As a renewable and abundant C1 resource possessing multiple attractive characteristics, such as low cost, nontoxicity, non-flammability, and easy accessibility, CO2 conversion into value-added chemicals and fuels can contribute to green chemistry and sustainable development. Since CO2 is a thermodynamically inert molecule, the activation of CO2 is pivotal for its effective conversion. In this regard, the formation of a transition-metal CO2 complex through direct coordination is one of the most powerful ways to induce the inert CO2 molecule to undergo chemical reactions. To date, numerous processes have been developed for efficient synthesis of cyclic carbonates from CO2 . On the basis of mechanistic understanding, we have developed efficient metal catalysts and green processes, including heterogeneous catalysis, and metal-free systems, such as ionic liquids, for cyclic carbonate synthesis. The big challenge is to develop catalysts that promote the reaction under low pressure (preferably at 1 bar). In this context, bifunctional catalysis is capable of synergistic activation of both the substrate and CO2 molecule, and thus, could render CO2 conversion smoothly under mild conditions. Alternatively, converting CO2 derivatives, that is, the captured CO2 as an activated species, would more easily take place at low pressure in comparison with gaseous CO2 . The aim of this Personal Account is to summarize versatile catalytic processes for cyclic carbonate synthesis from CO2 , including epoxide/CO2 coupling reaction, carboxylation of 1,2-diol with CO2 , oxidative cyclization of olefins with CO2 , condensation of vicinal halohydrin with CO2 , carboxylative cyclization of propargyl alcohols with CO2 , and conversion of the CO2 derivatives.

Cycloaddition of atmospheric CO2to epoxides under solvent-free conditions: a straightforward route to carbonates by green chemistry metrics

“…[1][2][3][4][5][6][7][8][9][10] Among various carbon dioxide xation reactions, cycloaddition of epoxides with CO 2 to ve-membered cyclic carbonates represents one of the most attractive, straightforward and green protocols. [11][12][13][14][15] Needless to say that ve-membered cyclic carbonate (1,3-dioxolan-2-one) is one of the most important O-heterocycles having increasing importance in medicinal chemistry [16][17][18] and organic synthesis. [19][20][21] The 1,3-dioxolan-2-one skeleton is also widely found in natural products (Scheme 1).…”

Experimental and theoretical study for CO2 activation and chemical fixation with epoxides

“…23,33,34 Thus the activation of CO 2 is pivotal for its effective conversion. The introduce/use of Lewis basic species and transition metal system have been highly considered, while the detailed CO 2 activation process was unclear, [35][36][37][38] so developing a catalytic system that provides molecular level insight for CO 2 activation process is still highly desired. Taking the aforementioned concerns into account, we propose to explore a new catalytic system that can activate and convert CO 2 with epoxides under mild conditions, and serve as an ideal mold for providing a detailed mechanistic understanding of CO 2 activation and xation process.…”

Hybrid Metalloporphyrin Magnetic Nanoparticles as Catalysts for Sequential Transformation of Alkenes and CO2 into Cyclic Carbonates

“…[1,2] In this context, conversion of carbon dioxide into valuableo rganic chemicals [3][4][5][6][7][8][9] has become at opicw ith increasing awareness,w ith remarkable economic and environmental impacts. Among numerousp ossible transformations, the cycloaddition of carbon dioxide to epoxidesi sa na tomeconomical approacht oprepare cyclic carbonates, [10][11][12][13] which has aw ide range of applications, namely as intermediates for fine chemicals or in the plastics industry,i nb iomedical applications, as electrolytes for lithium batteries, fuel additives, or green solvents. [14][15][16][17] So far,g reat effort has been devoted to the development of efficient catalytic systemsf or this conversion, [10,18,19] such as organocatalysts, [20][21][22] ionic liquids, [23,24] and metal catalysts, [25,31] namely those based on metalloporphyrins.…”