2026-04-05T10:53:05Zhttps://recercat.cat/oai/request

oai:recercat.cat:10256/197652024-12-17T14:27:03Zcom_2072_452955com_2072_2054col_2072_453073

Cycloaddition of CO2 to epoxides by highly nucleophilic 4-aminopyridines: establishing a relationship between carbon basicity and catalytic performance by experimental and DFT investigations Natongchai, Wuttichai Luque Urrutia, Jesús Antonio Phungpanya, Chalida Solà i Puig, Miquel D'Elia, Valerio Poater Teixidor, Albert Zipse, Hendrik Ciclització (Química) Catalitzadors Ring formation (Chemistry) Catalysts The development of single-component halogen-free organocatalysts in the highly investigated cyclo- addition of CO2 to epoxides is sought-after to enhance the sustainability of the process and reduce costs. In this context, the use of strongly nucleophilic single-component catalysts has been generally restricted to a limited selection of N-nucleophiles. In this study, predictive calculations of epoxide-specific carbon basicities suggested that highly nucleophilic 3,4-diaminopyridines possess suitable basicity to serve as active single-component catalysts for the cycloaddition of CO2 to epoxides. Indeed, experimentally, the most active compounds of this class performed efficiently for the conversion of epoxides to carbonates under atmospheric pressure outperforming the catalytic activity of traditional N-nucleophiles. Importantly, the 3,4-diaminopyridino scaffold could be easily supported on polystyrene and used as a recyclable heterogeneous catalyst under atmospheric CO2 pressure. Finally, the mechanism of the cyclo- addition reaction catalyzed by several N-nucleophiles was investigated highlighting the importance of the 3,4-diaminopyridine nucleophilicity in competently promoting the crucial initial step of epoxide ring- opening without the addition of nucleophiles or hydrogen bond donors A.P. and M.S. thank the Ministerio de Economía y Competitividad (MINECO) of Spain for projects CTQ2014-59832-JIN, PGC2018-097722-BI00 and CTQ2017-85341-P; Generalitat de Catalunya for project 2017SGR39, Xarxa de Referència en Química Teòrica i Computacional, and ICREA Academia prize 2014 to M.S. and 2019 to A.P 2024-06-18T13:56:38Z 2024-06-18T13:56:38Z info:eu-repo/date/embargoEnd/2022-02-06 2021-02-06 info:eu-repo/semantics/article info:eu-repo/semantics/acceptedVersion peer-reviewed http://hdl.handle.net/10256/19765 info:eu-repo/semantics/altIdentifier/doi/10.1039/D0QO01327G info:eu-repo/semantics/altIdentifier/eissn/2052-4129 info:eu-repo/grantAgreement/MINECO//CTQ2014-59832-JIN/ES/ESCANEO COMPUTACIONAL DE RELACIONES ESTRUCTURA%2FACTIVIDAD DE CATALIZADORES DE OXIDACION DEL AGUA PARA LA GENERACION DE H2/ info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2013-2016/CTQ2017-85341-P/ES/AVANCES EN LA REACTIVIDAD DE FULLERENOS Y NANOTUBOS: ESTUDIOS TEORICO-EXPERIMENTALES DE CICLACIONES CATALIZADAS POR METALES DE TRANSICION/ info:eu-repo/grantAgreement/AEI/Plan Estatal de Investigación Científica y Técnica y de Innovación 2017-2020/PGC2018-097722-B-I00/ES/REDESCUBRIMIENTO IN SILICO DE MECANISMOS ASISTIDOS DUALES DE LA CATALISIS MONOMETALICA: HACIA EL TRABAJO EN CONDICIONES SUAVES/ Tots els drets reservats info:eu-repo/semantics/openAccess Royal Society of Chemistry © Organic Chemistry Frontiers, 2021, vol. 8, p. 613-627 Articles publicats (D-Q) Natongchai, Wuttichai Luque Urrutia, Jesús Antonio Phungpanya, Chalida Solà i Puig, Miquel D'Elia, Valerio Poater Teixidor, Albert Zipse, Hendrik 2021 Cycloaddition of CO2 to epoxides by highly nucleophilic 4-aminopyridines: establishing a relationship between carbon basicity and catalytic performance by experimental and DFT investigations Organic Chemistry Frontiers 8 613 627