Computational analysis on the Pd-catalyzed C-N coupling of ammonia with aryl bromides using a chelate phosphine ligand
Gómez-Orellana Seguín, Pablo (Universitat Autònoma de Barcelona. Departament de Química)
Lledós, Agustí (Universitat Autònoma de Barcelona. Departament de Química)
Ujaque Pérez, Gregori (Universitat Autònoma de Barcelona. Departament de Química)

Data:	2021
Resum:	The Buchwald-Hartwig amination of arylhalides with the Pd-Josiphos complex is a very useful process for the generation of primary amines using ammonia as a reactant. Density-functional theory (DFT) calculations are carried out to examine the reaction mechanism for this process. Although the general mechanism for the C-N cross-coupling reaction is known, there are still some open questions regarding the effect of a chelate phosphine ligand and the role of the base in the process. Reaction pathways involving the release of one of the arms of the phosphine ligand are compared with those where the chelate phosphine remains fully coordinated. Conformational analysis for the complex with the open chelate phosphine is required to properly evaluate the proposed pathways. The role played by the added base (t-BuO-) as a possible ligand or just as a base was also evaluated. The understanding of all of these aspects allowed us to propose a complete reaction mechanism for the Pd-catalyzed C-N coupling of arylhalides with ammonia using the chelate Josiphos ligand.
Ajuts:	Agencia Estatal de Investigación CTQ2017-87889-P Ministerio de Economía y Competitividad CTQ2016-81797-REDC Ministerio de Economía y Competitividad BES-2015-07419
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Llengua:	Anglès
Document:	Article ; recerca ; Versió acceptada per publicar
Matèria:	DFT calculations ; C-N Coupling ; Pd catalyst ; Reaction Mechanism ; Ammonia
Publicat a:	Journal of organic chemistry, Vol. 86, Issue 5 (March 2021) , p. 4007-4017, ISSN 1520-6904

DOI: 10.1021/acs.joc.0c02865
PMID: 33592146

Postprint 14 p, 1.6 MB

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