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    Versatility of Boron-Mediated Coupling Reaction of Oxetanes and Epoxides with CO2: Selective Synthesis of Cyclic Carbonates or Linear Polycarbonates

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    Type
    Article
    Authors
    Zhang, Cheng Jian
    Wu, Shao Qi
    Boopathi, Senthil
    Zhang, Xing Hong cc
    Hong, Xin
    Gnanou, Yves cc
    Feng, Xiaoshuang
    KAUST Department
    Academic Affairs
    Chemical Science Program
    Office of the VP
    Physical Science and Engineering (PSE) Division
    Date
    2020-08-05
    Online Publication Date
    2020-08-05
    Print Publication Date
    2020-08-31
    Embargo End Date
    2021-08-05
    Submitted Date
    2020-06-29
    Permanent link to this record
    http://hdl.handle.net/10754/665752
    
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    Abstract
    Achieving simultaneously high selectivity and high rate in the coupling reaction of CO2 with poorly reacting oxetanes remains a major challenge. Here, the selective and nearly quantitative conversion of the coupling reaction of oxetanes with CO2 into six-membered cyclic organic carbonates (COCs) is described, when a binary metal-free system composed of commercially available alkyl borane and onium iodide salts is used under 10 bar CO2 pressure between 90 and 110 °C. Kinetic investigations provide quantitatively the enthalpy and entropy of activation [ΔH‡ = 6.7 ± 1.2 kcal/mol and ΔS‡ = -57 ± 4 cal/(mol·K)] of the back-biting, cyclic formation reaction. In addition to forming borate complexes with the anions responsible for the CO2/oxetane coupling reaction, these alkyl boranes activate the cyclic ethers as unambiguously confirmed by density functional theory studies. Upon selecting onium salts other than iodide-based ones, in particular those with poor leaving ability, the process is driven toward chain growth and the formation of linear polycarbonates. This metal-free system also exhibits both versatility and an activity comparable to that of metal catalysts (turnover frequency values of 14-124 h-1) for the synthesis of various five-membered COCs from epoxides and CO2.
    Citation
    Zhang, C.-J., Wu, S.-Q., Boopathi, S., Zhang, X.-H., Hong, X., Gnanou, Y., & Feng, X.-S. (2020). Versatility of Boron-Mediated Coupling Reaction of Oxetanes and Epoxides with CO2: Selective Synthesis of Cyclic Carbonates or Linear Polycarbonates. ACS Sustainable Chemistry & Engineering, 8(34), 13056–13063. doi:10.1021/acssuschemeng.0c04768
    Sponsors
    X.-H.Z. gratefully acknowledges financial support of the National Science Foundation of People’s Republic of China (nos. 51973190 and 21774108). X.H. is grateful for financial support from the National Natural Science Foundation of China (21702182, 21873081) and the Fundamental Research Funds for the Central Universities (2-2050205-19-361). C.-J.Z. acknowledges support of KAUST for his stay in Gnanou’s laboratory
    Publisher
    American Chemical Society (ACS)
    Journal
    ACS Sustainable Chemistry & Engineering
    DOI
    10.1021/acssuschemeng.0c04768
    Additional Links
    https://pubs.acs.org/doi/10.1021/acssuschemeng.0c04768
    ae974a485f413a2113503eed53cd6c53
    10.1021/acssuschemeng.0c04768
    Scopus Count
    Collections
    Articles; Physical Science and Engineering (PSE) Division; Chemical Science Program

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