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dc.contributor.authorDentoni Litta, Antonella
dc.contributor.authorBuonerba, Antonio
dc.contributor.authorCasu, Alberto
dc.contributor.authorFalqui, Andrea
dc.contributor.authorCapacchione, Carmine
dc.contributor.authorFranconetti, Antonio
dc.contributor.authorGarcia, Hermenegildo
dc.contributor.authorGrassi, Alfonso
dc.date.accessioned2021-06-02T07:59:32Z
dc.date.available2021-06-02T07:59:32Z
dc.date.issued2021-05-31
dc.identifier.citationDentoni Litta, A., Buonerba, A., Casu, A., Falqui, A., Capacchione, C., Franconetti, A., … Grassi, A. (2021). Highly Efficient Hydroamination of Phenylacetylenes with Anilines Catalysed by Gold Nanoparticles Embedded in Nanoporous Polymer Matrix: Insight into the Reaction Mechanism by Kinetic and DFT Investigations. Journal of Catalysis. doi:10.1016/j.jcat.2021.05.024
dc.identifier.issn0021-9517
dc.identifier.doi10.1016/j.jcat.2021.05.024
dc.identifier.urihttp://hdl.handle.net/10754/669343
dc.description.abstractThe synthesis of aromatic ketimines via hydroamination of phenylacetylenes (PAs) with anilines (ANs) has been accomplished in high yields and with excellent regio- and stereo-selectivity using gold nanoparticles (AuNPs) embedded in crystalline syndiotactic polystyrene-cis-1,4-polybutadiene (sPSB) multiblock copolymer matrix. The performances of the AuNPs-sPSB catalyst exceed those of the other commercial gold catalysts as a result of the physical chemical properties of the nanoporous polystyrenic support which allows excellent activity, thermal stability and recyclability of the catalyst. Electron donating (EDGs) and electron withdrawing (EWGs) substituents onto the aromatic group of ANs and PAs yield, in all examined cases, high selectivity in the formation of the thermodynamic favoured E stereoisomer of the aromatic ketimines. Kinetic investigation of the reaction mechanism in the presence of AN and of the deuterated analogue, AN-N,N-d2, highlighted a new reaction pathway for the hydroamination reaction, which was also supported by DFT calculations. Actually, the formation of AN aggregates stabilized by hydrogen bonding interactions produces a favourable transition state for the nucleophilic attack of AN to PA, coordinated/activated onto AuNPs surface. Moreover, an additional AN molecule cooperatively assists the 1,3-hydrogen shuttling from the N atom to the Cβ of the coordinated enamine intermediate to produce the kinetically favoured Z-ketimine intermediate that in turn evolves into the thermodynamically stable E-aromatic ketimine. The first order kinetics observed for AN, along with the experimental energetic barrier (ΔG‡ = 26.6±0.7 kcal mol−1; ΔH‡ = 13.4±1.8 kcal mol-1; ΔS‡ = -0.04±0.04 kcal mol-1 K-1) found in good agreement with the energy of the transition state calculated for the 1,3-hydrogen shift in the DFT modelling, strongly support that the latter is the rate determining step in the gold catalysed hydroamination of AN with PA.
dc.description.sponsorshipThe authors are grateful for funding from the Ministero dell'Università e della Ricerca - MIUR (PRIN2017 grant), and from the Università degli Studi di Salerno (FARB grants).
dc.publisherElsevier BV
dc.relation.urlhttps://linkinghub.elsevier.com/retrieve/pii/S0021951721002165
dc.rightsNOTICE: this is the author’s version of a work that was accepted for publication in Journal of Catalysis. Changes resulting from the publishing process, such as peer review, editing, corrections, structural formatting, and other quality control mechanisms may not be reflected in this document. Changes may have been made to this work since it was submitted for publication. A definitive version was subsequently published in Journal of Catalysis, [, , (2021-05)] DOI: 10.1016/j.jcat.2021.05.024 . © 2021. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
dc.titleHighly Efficient Hydroamination of Phenylacetylenes with Anilines Catalysed by Gold Nanoparticles Embedded in Nanoporous Polymer Matrix: Insight into the Reaction Mechanism by Kinetic and DFT Investigations
dc.typeArticle
dc.contributor.departmentBiological and Environmental Science and Engineering (BESE) Division
dc.contributor.departmentBioscience Program
dc.identifier.journalJournal of Catalysis
dc.rights.embargodate2022-05-01
dc.eprint.versionPost-print
dc.contributor.institutionDepartment of Chemistry and Biology “Adolfo Zambelli”, University of Salerno, Via Giovanni Paolo II, 84084, Fisciano (SA), Italy
dc.contributor.institutionInter-University Centre for Prediction and Prevention of Relevant Hazards (Centro Universitario per la Previsione e Prevenzione Grandi Rischi, C.U.G.RI.) and Sanitary Environmental Engineering Division (SEED), Department of Civil Engineering, University of Salerno, Via Giovanni Paolo II, 84084, Fisciano (SA), Italy
dc.contributor.institutionDepartamento de Química Orgánica, Facultad de Química, Universidad de Sevilla, C/ Profesor García González, 1, 41012, Sevilla, Spain
dc.contributor.institutionDepartamento de Quimica and Instituto Universitario de Tecnologia Quimica (CSIC-UPV), Universitat Politecnica de Valencia, Av. De los Naranjos s/n, 46022, Valencia, Spain
kaust.personCasu, Alberto
kaust.personFalqui, Andrea
dc.date.published-online2021-05-31
dc.date.published-print2021-08


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