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dc.contributor.authorZhang, Cheng Jian
dc.contributor.authorWu, Shao Qi
dc.contributor.authorBoopathi, Senthil
dc.contributor.authorZhang, Xing Hong
dc.contributor.authorHong, Xin
dc.contributor.authorGnanou, Yves
dc.contributor.authorFeng, Xiaoshuang
dc.date.accessioned2020-11-02T11:09:27Z
dc.date.available2020-11-02T11:09:27Z
dc.date.issued2020-08-05
dc.date.submitted2020-06-29
dc.identifier.citationZhang, 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
dc.identifier.issn2168-0485
dc.identifier.doi10.1021/acssuschemeng.0c04768
dc.identifier.urihttp://hdl.handle.net/10754/665752
dc.description.abstractAchieving 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.
dc.description.sponsorshipX.-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
dc.publisherAmerican Chemical Society (ACS)
dc.relation.urlhttps://pubs.acs.org/doi/10.1021/acssuschemeng.0c04768
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Sustainable Chemistry and Engineering, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acssuschemeng.0c04768.
dc.titleVersatility of Boron-Mediated Coupling Reaction of Oxetanes and Epoxides with CO2: Selective Synthesis of Cyclic Carbonates or Linear Polycarbonates
dc.typeArticle
dc.contributor.departmentAcademic Affairs
dc.contributor.departmentChemical Science Program
dc.contributor.departmentOffice of the VP
dc.contributor.departmentPhysical Science and Engineering (PSE) Division
dc.identifier.journalACS Sustainable Chemistry and Engineering
dc.rights.embargodate2021-08-05
dc.eprint.versionPost-print
dc.contributor.institutionMOE Key Laboratory of Macromolecular Synthesis and Functionalization, Department of Polymer Science and Engineering, Zhejiang University, Hangzhou 310027, China
dc.contributor.institutionDepartment of Chemistry, Zhejiang University, Hangzhou 310027, China
dc.identifier.volume8
dc.identifier.issue34
dc.identifier.pages13056-13063
kaust.personZhang, Cheng Jian
kaust.personBoopathi, Senthil
kaust.personGnanou, Yves
kaust.personFeng, Xiaoshuang
dc.date.accepted2020-07-23
dc.identifier.eid2-s2.0-85092338308
dc.date.published-online2020-08-05
dc.date.published-print2020-08-31


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