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Processes 2020, 8, 548 3 of 22 and agrochemicals, including vital precursors in organic synthesis [11]. Because of the low cost of the reaction, the Kolbe–Schmitt reaction is most stable and extensively used in industry, especially in the synthesis process of aspirin. Consequently, there is no considerable change that can be made to improve this reaction. In addition, the reaction of propargylic alcohol with CO2 to produce cyclic carbonate with the presence of base is applicable in industry (Figure 2; red box number 2) [11,12]. However, its industrial applicability on a larger scale is limited because of salt waste formation due to Processes 2020, 8, x FOR PEER REVIEW 3 of 22 the need of the acid addition to form free carboxylic acid [13]. Figure 2. Examples of CO2 as C1 feedstock in organic synthesis. The synthesis reactions marked with Figure 2. Examples of CO2 as C1 feedstock in organic synthesis. The synthesis reactions marked with red boxes have been industrialized [7–9]. red boxes have been industrialized [7–9]. This review focuses on the most prominent route, which is the cycloaddition of epoxides The Kolbe–Schmitt reaction (Figure 2; red box number 1) is one of the most essential and into CO2, producing cyclic carbonate and polymeric carbonate (Figure 2; red box number 3) [14]. renowned carboxylation reactions, offering an economical pathway to produce salicylic acids by The five-membered ring cyclic carbonates are extensively utilized as sustainable polar aprotic solvents, carboxylation of phenoxides with CO2 [10]. Salicylic acids are crucial chemicals in pharmaceuticals value-added compound for fuel, and electrolytes for lithium-ion batteries, and are the precursor for and agrochemicals, including vital precursors in organic synthesis [11]. Because of the low cost of the polymerization reactions and pharmaceuticals [15]. The CO2 coupling with epoxide captivates the reaction, the Kolbe–Schmitt reaction is most stable and extensively used in industry, especially in the interest of industries because of readily available precursors and widely used products that are cyclic synthesis process of aspirin. Consequently, there is no considerable change that can be made to carbonates [6]. Figure 3 shows typical and some emerging epoxide species, which can be classified as improve this reaction. In addition, the reaction of propargylic alcohol with CO2 to produce cyclic terminal epoxides (Figure 3a–g) and internal epoxides (Figure 3h–i). Their structure and abbreviations carbonate with the presence of base is applicable in industry (Figure 2; red box number 2) [11,12]. used in this manuscript are provided. However, its industrial applicability on a larger scale is limited because of salt waste formation due Ethylene carbonate and propylene carbonate are the most significant cyclic carbonates employed to the need of the acid addition to form free carboxylic acid [13]. in industry. They are commercially catalyzed by quaternary ammonium or phosphonium salts, which This review focuses on the most prominent route, which is the cycloaddition of epoxides into are relatively inefficient, and thus require high temperature and pressure [16]. For the past decades, CO2, producing cyclic carbonate and polymeric carbonate (Figure 2; red box number 3) [14]. The five- numerous catalysts, either homogeneous or heterogeneous, therefore have been extensively investigated. membered ring cyclic carbonates are extensively utilized as sustainable polar aprotic solvents, value- This paper aims to review recent advances and trends in catalytic CO2 cycloaddition, including added compound for fuel, and electrolytes for lithium-ion batteries, and are the precursor for homogeneous organocatalyst (e.g., organic salt, ionic liquid, deep eutectic solvents), organometallic polymerization reactions and pharmaceuticals [15]. The CO2 coupling with epoxide captivates the interest of industries because of readily available precursors and widely used products that are cyclic carbonates [6]. Figure 3 shows typical and some emerging epoxide species, which can be classified as terminal epoxides (Figure 3a–g) and internal epoxides (Figure 3h–i). Their structure and abbreviations used in this manuscript are provided. 1 2 3 Ethylene carbonate and propylene carbonate are the most significant cyclic carbonates employedPDF Image | Green Pathway Utilizing CO2 Cycloaddition Reaction Epoxide
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