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dc.contributor.author | Gil Ordóñez, Marta | |
dc.contributor.author | Maestro Fernández, Alicia | |
dc.contributor.author | Ortega, Pablo | |
dc.contributor.author | Jambrina, Pablo G. | |
dc.contributor.author | Andrés García, José María | |
dc.date.accessioned | 2021-12-09T12:32:53Z | |
dc.date.available | 2021-12-09T12:32:53Z | |
dc.date.issued | 2022 | |
dc.identifier.citation | Organic Chemistry Frontiers, 2022, vol. 9, n. 2, p. 420-427 | es |
dc.identifier.issn | 2052-4110 | es |
dc.identifier.uri | https://uvadoc.uva.es/handle/10324/50776 | |
dc.description | Producción Científica | es |
dc.description.abstract | Chiral 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.mimetype | application/pdf | es |
dc.language.iso | eng | es |
dc.publisher | Royal Society of Chemistry | es |
dc.rights.accessRights | info:eu-repo/semantics/openAccess | es |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/4.0/ | * |
dc.subject.classification | Pyrazolone | es |
dc.subject.classification | Pirazolona | es |
dc.title | NHC-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 stereoselectivity | es |
dc.type | info:eu-repo/semantics/article | es |
dc.rights.holder | © 2022 Royal Society of Chemistry | es |
dc.identifier.doi | 10.1039/D1QO01462E | es |
dc.relation.publisherversion | https://pubs.rsc.org/en/Content/ArticleLanding/2022/QO/D1QO01462E | es |
dc.peerreviewed | SI | es |
dc.description.project | Junta de Castilla y León (projects FEDER-VA115P17 and VA149G18) | es |
dc.description.project | Junta de Castilla y León (predoctoral fellowship EDU/556/2019) | es |
dc.description.project | Junta de Castilla y León - Fondo Social Europeo (grant EDU/601/2020) | es |
dc.description.project | Ministerio de Ciencia, Innovación y Universidades - Agencia Estatal de Investigación - Fundación Salamanca City of Culture and Knowledge (grant PID2020-113147GA-I00) | es |
dc.rights | Attribution-NonCommercial-NoDerivatives 4.0 Internacional | * |
dc.type.hasVersion | info:eu-repo/semantics/acceptedVersion | es |
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