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dc.contributor.author | Espinosa, M. | es_ES |
dc.contributor.author | Blay, G. | es_ES |
dc.contributor.author | Cardona, L. | es_ES |
dc.contributor.author | Fernández, I. | es_ES |
dc.contributor.author | Muñoz Roca, María Del Carmen | es_ES |
dc.contributor.author | Pedro, J.R. | es_ES |
dc.date.accessioned | 2020-06-11T03:33:46Z | |
dc.date.available | 2020-06-11T03:33:46Z | |
dc.date.issued | 2018 | es_ES |
dc.identifier.issn | 0095-8972 | es_ES |
dc.identifier.uri | http://hdl.handle.net/10251/145998 | |
dc.description | "This is an Accepted Manuscript of an article published by Taylor & Francis in Journal of Coordination Chemistry on 2018, available online: https://doi.org/10.1080/00958972.2018.1437422." | es_ES |
dc.description.abstract | [EN] In this paper, we report the application of chiral complexes of La(III) with pyBOX ligands as Lewis acid catalysts in the conjugate addition of malonic esters to N-tosyl imines derived from ß,gamma-unsaturated alfa-keto esters to give the corresponding chiral alfa,ß-dehydroamino esters. pyBOX complexes with La(III), Yb(III), Sc(III), and In(III) triflates were assessed in this reaction but only La(III) showed good activity and enantioselectivity, while Yb(III) provided the expected product with low yield and stereoselectivity, and the Sc(III) and In(III) complexes were completely inactive. The complex of La(OTf)3 with the diphenyl-pyBOX ligand prepared in situ provided the best results and allowed obtaining chiral ¿,ß-dehydroamino esters 3 with excellent yields, E:Z diastereomeric ratios (29:71-99:1) and high enantiomeric excesses (20-95%). The reaction could be applied to imines having a substituted aromatic ring or a heterocycle attached to the double bond, although the presence of electron-withdrawing groups on the aromatic ring was detrimental for stereoselectivity. The reaction products were obtained with the S configuration at the stereogenic center and the Z configuration at the enamine double bond as determined by NOESY experiments and X-ray analysis. Based on the experimental results a stereochemical model involving a nine-coordinate La(III) species has been proposed. | es_ES |
dc.description.sponsorship | This work was supported by the Ministerio de Economia y Competitividad (MINECO-Gobierno de Espana) [grant number CTQ2013-47494-P]. | es_ES |
dc.language | Inglés | es_ES |
dc.publisher | Taylor & Francis | es_ES |
dc.relation.ispartof | Journal of Coordination Chemistry | es_ES |
dc.rights | Reserva de todos los derechos | es_ES |
dc.subject | Asymmetric catalysis | es_ES |
dc.subject | Lanthanide complexes | es_ES |
dc.subject | Michael addition | es_ES |
dc.subject | Enantioselectivity | es_ES |
dc.subject.classification | FISICA APLICADA | es_ES |
dc.title | Lanthanum-pyBOX complexes as catalysts for the enantioselective conjugate addition of malonate esters to beta-gamma-unsaturated alfa-ketimino esters | es_ES |
dc.type | Artículo | es_ES |
dc.identifier.doi | 10.1080/00958972.2018.1437422 | es_ES |
dc.relation.projectID | info:eu-repo/grantAgreement/MINECO//CTQ2013-47494-P/ES/NUEVOS RETOS EN EL DESARROLLO DE PROCESOS ENANTIOSELECTIVOS DE FORMACION DE ENLACES C-C MEDIANTE CATALISIS DUAL COOPERATIVA./ | es_ES |
dc.rights.accessRights | Abierto | es_ES |
dc.contributor.affiliation | Universitat Politècnica de València. Departamento de Física Aplicada - Departament de Física Aplicada | es_ES |
dc.description.bibliographicCitation | Espinosa, M.; Blay, G.; Cardona, L.; Fernández, I.; Muñoz Roca, MDC.; Pedro, J. (2018). Lanthanum-pyBOX complexes as catalysts for the enantioselective conjugate addition of malonate esters to beta-gamma-unsaturated alfa-ketimino esters. Journal of Coordination Chemistry. 71(6):864-873. https://doi.org/10.1080/00958972.2018.1437422 | es_ES |
dc.description.accrualMethod | S | es_ES |
dc.relation.publisherversion | https://doi.org/10.1080/00958972.2018.1437422 | es_ES |
dc.description.upvformatpinicio | 864 | es_ES |
dc.description.upvformatpfin | 873 | es_ES |
dc.type.version | info:eu-repo/semantics/publishedVersion | es_ES |
dc.description.volume | 71 | es_ES |
dc.description.issue | 6 | es_ES |
dc.relation.pasarela | S\367523 | es_ES |
dc.contributor.funder | Ministerio de Economía y Competitividad | es_ES |
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dc.description.references | X-ray data for compound 3bl: crystallized from hexane-EtOAc; C25H29SN1O8; Mr = 503.55; triclinic; space group = P1; a = 6.2550(2), b = 10.2870(4), c = 11.1380(5) Å; α = 69.333(2), β = 78.688(2), γ = 82.555(2)°; V = 656.11(5) Å3; Z = 1; ρcalcd = 1.274 Mg m−3; μ = 0.170 mm−1; F(0 0 0) = 266. A colorless crystal of 0.04 × 0.08 × 0.08 mm3 was used; 5797 [R(int) = 0.0682] total reflections were collected on a Enraf Nonius Kappa CCD equipped with a graphite monochromator and Mo Kα (λ = 0.71073 Å) radiation. The structures were solved by using direct methods with SHELXS-2014 and refined by using full matrix least squares on F2 with SHELXL-2014 [16]. Non-hydrogen atoms were refined anisotropically and hydrogens were obtained or placed in calculated positions refined by using idealized geometries (riding model) and assigned fixed isotropic displacement parameters. Final values were R = 0.0469 and ωR = 0.1054. CCDC-1581116 contains the supplementary crystallographic data for this compound. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif. | es_ES |
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