Catalytic Strategies for the Cycloaddition of Pure, Diluted, and Waste CO₂ to Epoxides under Ambient Conditions

Abstract

Cyclic organic carbonates represent a relevant class of chemicals that can be prepared from CO 2 by cycloaddition to epoxides. The application of efficient catalysts is crucial in allowing the cycloaddition reaction to proceed under very mild conditions of temperature, pressure, and CO 2 concentration, thus resulting in a sustainable and carbonbalanced approach to CO 2 conversion. This is particularly the case if impure waste CO 2 could be employed as a feedstock. In this Review, we have critically analyzed the burgeoning literature on the cycloaddition of CO 2 to epoxides with the aim to provide state-of-the-art knowledge on the catalysts that can convert CO 2 to carbonates under ambient conditions. These have been systematically organized in families of compounds and critically scrutinized in terms of catalytic activity, availability and mechanistic features. Finally, we provide an overview on the catalytic systems able to function using diluted and impure CO 2 as a feedstock.

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

“…The crude was then purified by silica gel column chromatography,b yu sing dichloromethane/n-hexane (2:1) as the eluent. The complex 2-nitro-5,10,15,20-tetra-(4-trifluoromethylphenyl)porphyrinato copper(II) (9Cu)w as isolated in 84 2-Nitro-5,10,15,20-tetra(4-trifluoromethylphenyl)porphyrin (10) As olution of sulfuric acid 98 %( 10 mL) was added dropwise to a chloroform solution (200 mL) of 9Cu (500 mg, 0.50 mmol). The reaction was kept at 25 8Cf or 1h.T hen, the crude was carefully neutralized with as aturated solution of sodium bicarbonate and distilled water.T he organic solution was dried with anhydrous sodium sulfate.…”

“…[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. [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. [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.…”

“…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. [32][33][34][35][36][37][38][39][40][41][42][43] However,t he previous synthesis of epoxides often in-volve the use of toxic and expensiver eagents, andr equire hard separation/purification procedures.…”

Selective formation of a zwitterion adduct and bicarbonate salt in the efficient CO2 fixation by N-benzyl cyclic guanidine under dry and wet conditions

“…However, these kinds of catalysts often need high temperatures and pressure to completely achieve the CO 2 fixation [6]. On the other hand, amidine and guanidine derivatives are well known as efficient catalysts for the cycloaddition of CO 2 to epoxides at ambient temperature [7,14–18]. Previously, we reported that hydroiodides of amidine derivatives worked as significantly efficient catalysts for the cycloaddition of CO 2 to epoxides under ambient temperature and pressure [19–22].…”

Insights into the Base‐Assisted Acrylate Formation from CO2/C2H4 Coupling by Pd‐ and Ni‐catalyst: A DFT Mechanistic Study

“…[5] One promising method is to couple CO 2 with high-energy molecules like epoxides, alkynes and olefins to form useful monomers. [6] Among them, the oxidative coupling of carbon dioxide with ethylene to synthesize acrylic acid and derivatives is of high interest because of the wide application of acrylic acid and derivatives in chemical industry (e. g. plastics, textiles, coatings, elastomers, adhesives, and paints). [7] In particular, the global annual demanding for sodium acrylate alone is 4 million tons.…”