2026-04-17T16:16:42Zhttps://recercat.cat/oai/request

oai:recercat.cat:10256/196882024-06-18T13:56:32Zcom_2072_452955com_2072_2054col_2072_453073

2024-06-18T13:56:32Z urn:hdl:10256/19688 Double-Carrousel Mechanism for Mn-Catalyzed Dehydrogenative Amide Synthesis from Alcohols and Amines Luque Urrutia, Jesús Antonio Pèlachs, Tània Solà i Puig, Miquel Poater Teixidor, Albert Amides -- Síntesi Amides -- Synthesis Catalitzadors Catalysts We study with density functional theory calculations the mechanism of the original example of a base-metal-catalyzed synthesis of amides from alcohols and amines. A preliminary proposal of the mechanism of this reaction was experimentally reported by Milstein and co-workers. Instead of the proposed reaction mechanism with a hemilabile pincer amine arm, our DFT calculations describe a facile protocol, where the catalyst only produces aldehydes from alcohols. Once formaldehyde is formed from methanol, it reacts with the amine to form a second alcohol. This new alcohol undergoes the same procedure as methanol and creates the desired amide through a double-carrousel mechanism. The rate-determining step in the catalytic aldehyde synthesis corresponds to the H2 formation. However, in the nonmetal-catalyzed part of the mechanism, the interaction of formaldehyde with the amine is also quite kinetically demanding J.A.L.-U. thanks Universitat de Girona for an IFUdG2017 Ph.D. fellowship. A.P. is a Serra Húnter Fellow. A.P. and M.S. thank the Ministerio de Economía y Competitividad (MINECO) of Spain for projects PGC2018-097722-B-I00 and CTQ2017-85341-P; Generalitat de Catalunya for project 2017SGR39 and ICREA Academia prize 2019 to A.P. 2024-06-18T13:56:32Z 2024-06-18T13:56:32Z info:eu-repo/date/embargoEnd/2022-05-06 2021-05-06 info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion peer-reviewed http://hdl.handle.net/10256/19688 info:eu-repo/semantics/altIdentifier/doi/10.1021/acscatal.1c00693 info:eu-repo/semantics/altIdentifier/eissn/2155-5435 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/ 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/ Reconeixement 4.0 Internacional http://creativecommons.org/licenses/by/4.0 info:eu-repo/semantics/openAccess American Chemical Society ACS Catalysis, 2021, vol.11, núm. 10, p. 6155-6161 Articles publicats (D-Q)