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dc.contributor.author | Blay, G. | es_ES |
dc.contributor.author | Cano, J. | es_ES |
dc.contributor.author | Cardona, L. | es_ES |
dc.contributor.author | Fernandez, I. | es_ES |
dc.contributor.author | Muñoz Roca, María del Carmen | es_ES |
dc.contributor.author | Pedro, J.R. | es_ES |
dc.contributor.author | Vila, C. | es_ES |
dc.date.accessioned | 2015-12-22T07:48:26Z | |
dc.date.issued | 2012-12-07 | |
dc.identifier.issn | 0022-3263 | |
dc.identifier.uri | http://hdl.handle.net/10251/59125 | |
dc.description.abstract | Experimental and theoretical studies on the structure of several complexes based on (R)-3,3'-Br-2-BINOL ligand and group (IV) metals used as catalysts in an enantioselective Friedel-Crafts alkylation of indoles with alpha,beta-unsaturated ketones have been carried out. NMR spectroscopic studies of these catalysts have been performed, which suggested that at room temperature the catalysts would form a monomeric structure in the case of Ti-IV and a dimeric structure in the cases of Zr-IV and Hf-IV. Density functional theory (DFT) calculations clearly corroborate the conclusions of these experimental spectroscopic studies. The dimeric structure with a doubly bridged motif [Zr-2(IV)(mu-(R)-3,3'-Br-2-BINOL)(2)] where each binaphthol ligand acts as bridge between the metal centers (Novak's model) is more stable than the dimeric structure with a doubly bridged motif [Zr-2(IV)(mu-(OBu)-Bu-t)(2)] where the tert-butoxide groups act as bridging ligands (Kobayashi's model). The scope of the Friedel-Crafts alkylation with regard to the indole structure has been studied. Finally a plausible mechanism for the Friedel-Crafts reaction and a stereomodel for the mode of action of the catalyst that explain the observed stereochemistry of the reaction products have been proposed. | es_ES |
dc.description.sponsorship | Financial support from the Ministerio de Ciencia e Innovacion, Gobierno de Espana and FEDER, European Union (Grant CTQ 2009-13083) and the Generalitat Valenciana (Grants ACOMP/2012/212 and ISIC 2012/001) is acknowledged. C.V. thanks the Generalitat Valenciana for a predoctoral grant | en_EN |
dc.language | Español | es_ES |
dc.publisher | American Chemical Society | es_ES |
dc.relation.ispartof | Journal of Organic Chemistry | es_ES |
dc.rights | Reserva de todos los derechos | es_ES |
dc.subject.classification | FISICA APLICADA | es_ES |
dc.title | NMR Spectrocopic Characterization and DFT Calculations of Zirconium(IV)-3,3 -Br-2-BINOLate and Related Complexes Used in an Enantioselective Friedel Crafts Alkylation of Indoles with alpha, beta-Unsaturated Ketones | es_ES |
dc.type | Artículo | es_ES |
dc.embargo.lift | 10000-01-01 | |
dc.embargo.terms | forever | es_ES |
dc.identifier.doi | 10.1021/jo3013594 | |
dc.relation.projectID | info:eu-repo/grantAgreement/MICINN//CTQ2009-13083/ES/Desarrollo de nuevos procesos enantioselectivos de formación de enlaces C-C mediante catálisis asimétrica/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/GVA//ISIC%2F2012%2F001/ | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/GVA//ACOMP%2F2012%2F212/ | es_ES |
dc.rights.accessRights | Cerrado | es_ES |
dc.contributor.affiliation | Universitat Politècnica de València. Departamento de Física Aplicada - Departament de Física Aplicada | es_ES |
dc.description.bibliographicCitation | Blay, G.; Cano, J.; Cardona, L.; Fernandez, I.; Muñoz Roca, MDC.; Pedro, J.; Vila, C. (2012). NMR Spectrocopic Characterization and DFT Calculations of Zirconium(IV)-3,3 -Br-2-BINOLate and Related Complexes Used in an Enantioselective Friedel Crafts Alkylation of Indoles with alpha, beta-Unsaturated Ketones. Journal of Organic Chemistry. 77(23):10545-10556. https://doi.org/10.1021/jo3013594 | es_ES |
dc.description.accrualMethod | S | es_ES |
dc.relation.publisherversion | http://dx.doi.org/10.1021/jo3013594 | es_ES |
dc.description.upvformatpinicio | 10545 | es_ES |
dc.description.upvformatpfin | 10556 | es_ES |
dc.type.version | info:eu-repo/semantics/publishedVersion | es_ES |
dc.description.volume | 77 | es_ES |
dc.description.issue | 23 | es_ES |
dc.relation.senia | 232408 | es_ES |
dc.contributor.funder | Ministerio de Ciencia e Innovación | es_ES |
dc.contributor.funder | Generalitat Valenciana | es_ES |
dc.contributor.funder | European Regional Development Fund | es_ES |