Synergistic effect of a binary ionic liquid/base catalytic system for efficient conversion of epoxide and carbon dioxide into cyclic carbonates

Mujmule, Rajendra B.; Rao, M. P.; Rathod, Pramod V.; Deonikar, Virendrakumar G.; Chaugule, Avinash A.; Kim, Hern

doi:10.1016/j.jcou.2019.06.013

Cited by 32 publications

(9 citation statements)

References 33 publications

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“…The slightly reduced conversion value with respect to the cycloaddition of propylene oxide may be due to the deviation of the experiment for a solvent-free reaction and volatilization due to its lower boiling point. In general, all of these CO 2 addition reactions bearing the NIR photothermal condition at less elevated temperature and atmospheric pressure achieve similar levels in yield and selectivity as those reported in other works at higher temperatures and raised pressures. ,, …”

Section: Resultssupporting

confidence: 72%

Near-Infrared Photothermal Catalysis for Enhanced Conversion of Carbon Dioxide under Mild Conditions

Chen

Wei

Yang

et al. 2022

ACS Appl. Mater. Interfaces

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Enhanced conversion of carbon dioxide (CO2) for cycloaddition with epoxide derivatives is highly desired in organic synthesis and green chemistry, yet it is still a challenge to obtain satisfactory activity under mild reaction conditions of temperature and pressure. For this purpose, an unexploited strategy is proposed here by incorporating near-infrared (NIR) photothermal properties into multicomponent catalysts. Through the electrostatic adsorption of Co- or Ce-substituted polyoxometalate (POM) clusters on the surface of graphene oxide (GO) with covalently grafted polyethyleneimine (PEI), a series of composite catalysts POMs@GO-PEI are prepared. The structural and property characterizations demonstrate the synergistic advantages of the catalysts bearing Lewis acids and bases and local NIR photothermal heating from the GO matrix for dramatically enhanced CO2 cycloaddition. Noticeably, while the turnover frequency increases up to 2718 h–1, the heterogeneous catalysts exhibit photothermal stability and recyclability. With this method, the onsite NIR photothermal transformation becomes extendable to more green reaction processes.

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Section: Resultssupporting

confidence: 72%

Near-Infrared Photothermal Catalysis for Enhanced Conversion of Carbon Dioxide under Mild Conditions

Chen

Wei

Yang

et al. 2022

ACS Appl. Mater. Interfaces

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“…[EvimOH] chloride and DBU provided the most active system. 102 This binary catalyst gave 76-99% yields for six simple terminal epoxides, and even gave 76% yield when ring-opening cyclohexene oxide 1, using <2 mol% of ionic liquid and base, at 20 bar of carbon Please do not adjust margins Please do not adjust margins dioxide at 120 o C for 1-8 h. This catalyst also maintained consistent activity after five uses and it was proposed that the reaction occurred via carbon dioxide activation (Scheme 5).…”

Section: Organic Salts and Organic Basesmentioning

confidence: 89%

Recent developments in organocatalysed transformations of epoxides and carbon dioxide into cyclic carbonates

2021

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“…Carbon dioxide (CO 2 ) is an abundant, nontoxic, and easily available and renewable C1 resource. − Therefore, transforming of CO 2 into value-added organic compounds is a very important research topic in green and sustainable chemistry. − Recently, ionic liquids (ILs) have been identified for their outstanding performance in CO 2 transformation due to their unique properties such as good thermal stability and tunability. , Many strategies have been employed for the IL-promoted the transformation of CO 2 into various high-value chemicals such as cyclic carbonates, − oxazolidinones, − quinazoline-2,4(1 H ,3 H )-diones, − α-hydroxy ketones, et al Among these strategies, the fabrication of α-alkylidene cyclic carbonates through the IL-catalyzed carboxylative cyclization of propargylic alcohols (PAs) with CO 2 which was first published by Liu and co-workers in 2016 is extremely efficient, making it highly desirable for industry applications. , After that, many kinds of ILs were used to improve the performance of this reaction. By screening various available ILs employed in the reaction between PA and CO 2 , the azole-anion-based ILs (AILs) such as [P 4444 ][Im], [P 4444 ][2-MeIm], [P 4444 ][4-MeIm], [P 4444 ][2,4-DMeIm], [DBUH][2-MeIm], et al exhibited better catalytic performance than the other ILs .…”

Section: Introductionmentioning

confidence: 99%

Insight into the Interactions between Azole-Anion-Based Ionic Liquids and Propargylic Alcohol: Influence on the Carboxylative Cyclization of Propargylic Alcohol with Carbon Dioxide

Tang

Lü

et al. 2021

ACS Sustainable Chem. Eng.

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To reveal the interactions between azole-anionbased ionic liquids (AILs) and propargyl alcohol (PA) and their effect on the carboxylative cyclization reaction of PA with CO 2 , three AILs, namely, [P 66614 ][Im], [P 66614 ][4-MeIm], and [P 66614 ][4-BrIm], were synthesized and characterized. The interactions between the AILs with 2-methyl-3-butyn-2-ol (MBY) were investigated through IR and 1 H NMR spectra and DFT calculations. The results indicate that azole-based anions can form H-bonds with the hydroxyl (O−H) and the alkynyl hydrogen atoms (CC−H) of MBY simultaneously, with the former much stronger than the latter, which is supported by the interaction energy and the distance of the H-bond from DFT calculations. Interestingly, the strength of the former always increases with the mole fraction of AIL (x AIL ), while that of the latter first decreases and then increases, reaching a minimum at x AIL ≈ 0.4. Furthermore, the order of the strength of the two H-bonds is as follows:which is in good agreement with their basicity. According to the interactions between the AILs with MBY and combined with the reaction mechanism of MBY with CO 2 promoted by AILs, it is evident that the increase in the basicity of the AILs enhances the H-bond between the AILs with O−H, thereby enhancing the activation of MBY and the subsequent CO 2 conversion. However, this will also increase the interaction between AILs and CC−H, resulting in the deprotonation of CC−H and hindering the activation of MBY. Therefore, choosing a suitable basic AIL and controlling its ratio are the keys to the reaction of PA and CO 2 .

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Synergistic effect of a binary ionic liquid/base catalytic system for efficient conversion of epoxide and carbon dioxide into cyclic carbonates

Cited by 32 publications

References 33 publications

Near-Infrared Photothermal Catalysis for Enhanced Conversion of Carbon Dioxide under Mild Conditions

Near-Infrared Photothermal Catalysis for Enhanced Conversion of Carbon Dioxide under Mild Conditions

Recent developments in organocatalysed transformations of epoxides and carbon dioxide into cyclic carbonates

Insight into the Interactions between Azole-Anion-Based Ionic Liquids and Propargylic Alcohol: Influence on the Carboxylative Cyclization of Propargylic Alcohol with Carbon Dioxide

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