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dc.contributor.authorGil Ordóñez, Marta 
dc.contributor.authorMaestro Fernández, Alicia 
dc.contributor.authorOrtega, Pablo
dc.contributor.authorJambrina, Pablo G.
dc.contributor.authorAndrés García, José María 
dc.date.accessioned2021-12-09T12:32:53Z
dc.date.available2021-12-09T12:32:53Z
dc.date.issued2022
dc.identifier.citationOrganic Chemistry Frontiers, 2022es
dc.identifier.issn2052-4110es
dc.identifier.urihttps://uvadoc.uva.es/handle/10324/50776
dc.descriptionProducción Científicaes
dc.description.abstractChiral pyrazolones with a spirocyclic centre at the C4-position are widely found in a large family of medically relevant compounds. In recent years, organocatalysis, particularly that performed with quiral N-heterocyclic carbenes (NHCs), has allowed the enantioselective synthesis of these spirocyclic compounds despite its inherent difficulty. In this work, we describe the fully diastereo- and highly enantioselective synthesis of novel spirocyclic pyrazolone γ-butyrolactones via NHC-catalysed [3+2] annulation reaction of enals and 1H-pyrazol-4,5-diones. To understand the catalytic mechanism and origin of stereoselectivity, electronic structure calculations were carried out. After considering various pathways, we concluded that stereoselectivity-determining step is the formation of the lactone that proceeds after addition of the NHC derived homoenolate to the electrophilic carbonyl group of pyrazolin-4,5-dione. Our calculations predict that the free energy barrier is lower for the (RS) product, which is also the main product experimentally obtained.es
dc.format.mimetypeapplication/pdfes
dc.language.isoenges
dc.publisherRoyal Society of Chemistryes
dc.rights.accessRightsinfo:eu-repo/semantics/embargoedAccesses
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/*
dc.subject.classificationPyrazolonees
dc.subject.classificationPirazolonaes
dc.titleNHC-Catalysed [3+2]-Asymmetric Annulation between Pyrazolin-4,5-diones and Enals: Synthesis of Novel Spirocyclic Pyrazolone γ-Butyrolactones and Computational Study of Mechanism and Stereoselectivityes
dc.typeinfo:eu-repo/semantics/articlees
dc.rights.holder© 2022 Royal Society of Chemistryes
dc.identifier.doi10.1039/D1QO01462Ees
dc.relation.publisherversionhttps://pubs.rsc.org/en/Content/ArticleLanding/2022/QO/D1QO01462Ees
dc.peerreviewedSIes
dc.description.projectJunta de Castilla y León (projects FEDER-VA115P17 and VA149G18)es
dc.description.projectJunta de Castilla y León (predoctoral fellowship EDU/556/2019)es
dc.description.projectJunta de Castilla y León - Fondo Social Europeo (grant EDU/601/2020)es
dc.description.projectMinisterio de Ciencia, Innovación y Universidades - Agencia Estatal de Investigación - Fundación Salamanca City of Culture and Knowledge (grant PID2020-113147GA-I00)es
dc.rightsAttribution-NonCommercial-NoDerivatives 4.0 Internacional*
dc.type.hasVersioninfo:eu-repo/semantics/acceptedVersiones


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