Articles producció científica> Química Física i Inorgànica

Iridium-Catalyzed Asymmetric Hydrogenation with Simple Cyclohexane-Based P/S Ligands: In Situ HP-NMR and DFT Calculations for the Characterization of Reaction Intermediates

  • Datos identificativos

    Identificador: PC:1255
    Autores:
    Montserrat DiéguezOscar PàmiesMARIA BIOSCACarlota Borràs
    Resumen:
    We report a reduced but structurally valuable phosphite/phosphinite-thioether ligand library for the Irhydrogenation of 40 minimally functionalized alkenes, including relevant examples with poorly coordinative groups. We found that enantiomeric excesses are mainly dependent on the substrate structure and on some ligand parameters (i.e., the type of thioether/phosphorus moieties and the configuration of the phosphite group), whereas the substituents of the biaryl phosphite moiety had little impact. By tuning the ligand parameters we were able to find highly selective catalysts for a range of substrates (ee’s up to 99%). These phosphite/phosphinite-thioether ligands have a simple backbone and thus yield simple NMR spectra that reduce signal overlap and facilitate the identification of relevant intermediates. Therefore, by combining HP-NMR spectroscopy and theoretical studies, we were also able to identify the catalytically competent Ir-dihydride alkene species, which made it possible to explain the enantioselectivity obtained.
  • Otros:

    Autor según el artículo: Montserrat Diéguez Oscar Pàmies MARIA BIOSCA Carlota Borràs
    Departamento: Química Física i Inorgànica
    Autor/es de la URV: DIÉGUEZ FERNÁNDEZ, MONTSERRAT PAMIES OLLÉ, OSCAR MARIA BIOSCA BORRÀS NOGUERA, CARLOTA
    Palabras clave: reaction intermediates asymmetric catalysis iridium
    Resumen: We report a reduced but structurally valuable phosphite/phosphinite-thioether ligand library for the Irhydrogenation of 40 minimally functionalized alkenes, including relevant examples with poorly coordinative groups. We found that enantiomeric excesses are mainly dependent on the substrate structure and on some ligand parameters (i.e., the type of thioether/phosphorus moieties and the configuration of the phosphite group), whereas the substituents of the biaryl phosphite moiety had little impact. By tuning the ligand parameters we were able to find highly selective catalysts for a range of substrates (ee’s up to 99%). These phosphite/phosphinite-thioether ligands have a simple backbone and thus yield simple NMR spectra that reduce signal overlap and facilitate the identification of relevant intermediates. Therefore, by combining HP-NMR spectroscopy and theoretical studies, we were also able to identify the catalytically competent Ir-dihydride alkene species, which made it possible to explain the enantioselectivity obtained.
    Grupo de investigación: Organometàl.lics i Catàlisi Homogènia
    Áreas temáticas: Chemistry Química Química
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 0276-7333
    Identificador del autor: 0000-0002-8450-0656 0000-0002-2352-8508 n/a n/a
    Fecha de alta del registro: 2015-11-18
    Página final: 5334
    Volumen de revista: 34
    Versión del articulo depositado: info:eu-repo/semantics/acceptedVersion
    Enlace a la fuente original: https://pubs.acs.org/doi/10.1021/acs.organomet.5b00790
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    DOI del artículo: 10.1021/acs.organomet.5b00790
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2015
    Página inicial: 5321
    Tipo de publicación: Post-print
  • Palabras clave:

    Catàlisi asimètrica
    Iridi
    reaction intermediates
    asymmetric catalysis
    iridium
    Chemistry
    Química
    Química
    0276-7333
  • Documentos:

  • Cerca a google

    Search to google scholar