2026-04-13T00:51:02Zhttps://recercat.cat/oai/requestoai:recercat.cat:10256/196882024-06-18T13:56:32Zcom_2072_452955com_2072_2054col_2072_453073
RECERCAT
author
Luque Urrutia, Jesús Antonio
author
Pèlachs, Tània
author
Solà i Puig, Miquel
author
Poater Teixidor, Albert
2024-06-18T13:56:32Z
2024-06-18T13:56:32Z
info:eu-repo/date/embargoEnd/2022-05-062021-05-06
http://hdl.handle.net/10256/19688
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 demandingJ.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.
Reconeixement 4.0 Internacional http://creativecommons.org/licenses/by/4.0 info:eu-repo/semantics/openAccess
Amides -- Síntesi
Amides -- Synthesis
Catalitzadors
Catalysts
Double-Carrousel Mechanism for Mn-Catalyzed Dehydrogenative Amide Synthesis from Alcohols and Amines
info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion peer-reviewed