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Theoretical study on the molecular mechanism of the [5 + 2] vs. [4 + 2] cyclization mediated by Lewis acid in the quinone system

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Theoretical study on the molecular mechanism of the [5 + 2] vs. [4 + 2] cyclization mediated by Lewis acid in the quinone system

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dc.contributor.author Soto-Delgado, Jorge es_ES
dc.contributor.author Sáez-Cases, José Antonio es_ES
dc.contributor.author Tapia, Ricardo A. es_ES
dc.contributor.author Domingo, Luis R. es_ES
dc.date.accessioned 2017-07-17T10:41:27Z
dc.date.available 2017-07-17T10:41:27Z
dc.date.issued 2013-10-28
dc.identifier.issn 1477-0520
dc.identifier.uri http://hdl.handle.net/10251/85252
dc.description.abstract [EN] The thermal and Lewis acid (LA) catalyzed cyclizations of quinone 1 involved in the synthesis of Colombiasin A and Elipsaterosin B have been theoretically studied using DFT methods at the B3LYP/6-311G(d,p) computational level. B3LYP calculations suggest that the formal endo [4 + 2] cycloadduct allowing the synthesis of Colombiasin A is preferentially formed under thermal conditions, while in the presence of the BF3 LA catalyst the formal [5 + 2] cycloadduct is seen, allowing the synthesis of Elipsaterosin B. The BF3 LA catalyst not only accelerates the nucleophilic attack on the C2 carbon of the quinone framework through a more polar C-C bond formation, but also provokes a different electron density rearrangement along the nucleophilic attack favoring the subsequent C-C bond formation at the C4 carbon with the formation of the formal [5 + 2] cycloadduct. ELF bonding analysis along these cyclizations indicates that the C-C single bond formation takes place in the range of 1.91-2.1 angstrom by C-to-C coupling of two pseudoradical centers. Along the formation of the first C2-C9 single bond, these pseudoradical centers appear at one of the most electrophilic and at one of the most nucleophilic centers of quinone 1, C2 and C9 carbons, respectively. Analysis of the Parr functions suggests that although the most favorable electrophilic/nucleophilic interaction is that involving the C2 carbon of quinone and the C12 carbon of the butadiene framework, the intramolecular nature of the cyclization prevents the corresponding reactive channel. es_ES
dc.description.sponsorship This work was supported by the Post-Doctoral fellow FONDECYT Grant 3130359 and Project ICM-P10-003-F CILIS granted by Fondo de Innovacion para la Competitividad del Ministerio de Economia, Fomento y Turismo, Chile.
dc.language Inglés es_ES
dc.publisher Royal Society of Chemistry es_ES
dc.relation Ministerio de Economía, Fomento y Turismo, Chile/ICM-P10-003-F CILIS es_ES
dc.relation FONDECYT/3130359
dc.relation.ispartof Organic and Biomolecular Chemistry es_ES
dc.rights Reserva de todos los derechos es_ES
dc.subject Electron localization function es_ES
dc.subject Polarizable continuum model es_ES
dc.subject Diels-alder reaction es_ES
dc.subject Topological analysis es_ES
dc.subject Bond formation es_ES
dc.subject Elf analysis es_ES
dc.subject Cycloaddition reaction es_ES
dc.subject (-) Elisapterosin-B es_ES
dc.subject (-) Colombiasin-A es_ES
dc.title Theoretical study on the molecular mechanism of the [5 + 2] vs. [4 + 2] cyclization mediated by Lewis acid in the quinone system es_ES
dc.type Artículo es_ES
dc.identifier.doi 10.1039/c3ob41860j
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 Soto-Delgado, J.; Sáez-Cases, JA.; Tapia, RA.; Domingo, LR. (2013). Theoretical study on the molecular mechanism of the [5 + 2] vs. [4 + 2] cyclization mediated by Lewis acid in the quinone system. Organic and Biomolecular Chemistry. 11(48):8357-8365. doi:10.1039/c3ob41860j es_ES
dc.description.accrualMethod S es_ES
dc.relation.publisherversion http://doi.org/10.1039/c3ob41860j es_ES
dc.description.upvformatpinicio 8357 es_ES
dc.description.upvformatpfin 8365 es_ES
dc.type.version info:eu-repo/semantics/publishedVersion es_ES
dc.description.volume 11 es_ES
dc.description.issue 48 es_ES
dc.relation.senia 256844 es_ES
dc.identifier.eissn 1477-0539
dc.identifier.pmid 24170110
dc.contributor.funder Fondo Nacional de Desarrollo Científico y Tecnológico, Chile
dc.contributor.funder Ministerio de Economía, Fomento y Turismo, Chile


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