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A theoretical study on NHC-catalysed enantioselective cycloaddition of ketenes and 3-aroylcoumarins: mechanism and enantioselectivity

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A theoretical study on NHC-catalysed enantioselective cycloaddition of ketenes and 3-aroylcoumarins: mechanism and enantioselectivity

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dc.contributor.author Zaragoza, Ramón J. es_ES
dc.contributor.author Aurell, Maria J. es_ES
dc.contributor.author González-Cardenete, Miguel A es_ES
dc.date.accessioned 2019-09-14T20:01:09Z
dc.date.available 2019-09-14T20:01:09Z
dc.date.issued 2018 es_ES
dc.identifier.issn 1477-0520 es_ES
dc.identifier.uri http://hdl.handle.net/10251/125677
dc.description.abstract [EN] The NHC-catalysed enantioselective cycloaddition of ketenes to 3-aroylcoumarins to yield dihydrocoumarin-fused dihydropyranones has been investigated using DFT methods at the B3LYP/6-31G* and MPWB1K/6-311G** computational levels. Two plausible mechanisms have been studied: the ¿ketene-first¿ mechanism A and the ¿coumarin-first¿ mechanism B. An analysis of the activation Gibbs free energies involved in the two competitive pathways makes it possible to rule out the pathway associated with the ¿coumarin-first¿ mechanism B. The first step of the ¿ketene-first¿ mechanism A is the formation of zwitterionic intermediate IN1-Z via nucleophilic attack of NHC 1 to ketene 2. [4+2] cycloaddition through nucleophilic attack of enolate IN1-Z to the conjugate double bond of benzoyl group of the coumarin 3, via TS3-SS-a2 or TS3-RR-a2, yield IN3. Finally the extrusion of catalyst through TS5 leads to the final products either 4-SS or 4-RR. Enantioselectivity observed in the experimental results is determined in the transition states TS3-SS-a2/ TS3-RR-a2. In this path, the intramolecular hydrogen-bonding between the hydroxyl group of the IN1-Z adduct and the carbonyl oxygen of the original ketene group directs the final stereochemistry throughout the entire process. es_ES
dc.description.sponsorship This study was supported by intramural grant 201680I008 from the Spanish Government (Consejo Superior de Investigaciones Cientificas). es_ES
dc.language Inglés es_ES
dc.publisher The Royal Society of Chemistry es_ES
dc.relation.ispartof Organic & Biomolecular Chemistry es_ES
dc.rights Reserva de todos los derechos es_ES
dc.subject Carbene es_ES
dc.subject Enantioselective es_ES
dc.subject Ketene es_ES
dc.subject Aroylcoumarin es_ES
dc.subject DFT es_ES
dc.title A theoretical study on NHC-catalysed enantioselective cycloaddition of ketenes and 3-aroylcoumarins: mechanism and enantioselectivity es_ES
dc.type Artículo es_ES
dc.identifier.doi 10.1039/c8ob01035h es_ES
dc.relation.projectID info:eu-repo/grantAgreement/COLCIENCIAS//RC648-2017/ es_ES
dc.relation.projectID info:eu-repo/grantAgreement/CSIC//2001680I008/ es_ES
dc.rights.accessRights Abierto es_ES
dc.contributor.affiliation Universitat Politècnica de València. Instituto Universitario Mixto de Tecnología Química - Institut Universitari Mixt de Tecnologia Química es_ES
dc.description.bibliographicCitation Zaragoza, RJ.; Aurell, MJ.; González-Cardenete, MA. (2018). A theoretical study on NHC-catalysed enantioselective cycloaddition of ketenes and 3-aroylcoumarins: mechanism and enantioselectivity. Organic & Biomolecular Chemistry. 16(30):5474-5482. https://doi.org/10.1039/c8ob01035h es_ES
dc.description.accrualMethod S es_ES
dc.relation.publisherversion http://doi.org/10.1039/c8ob01035h es_ES
dc.description.upvformatpinicio 5474 es_ES
dc.description.upvformatpfin 5482 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 16 es_ES
dc.description.issue 30 es_ES
dc.identifier.pmid 30022178
dc.relation.pasarela S\368011 es_ES
dc.contributor.funder Consejo Superior de Investigaciones Científicas es_ES
dc.contributor.funder Departamento Administrativo de Ciencia, Tecnología e Innovación, Colombia es_ES
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