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

  • Dades identificatives

    Identificador: PC:1255
    Handle: https://hdl.handle.net/20.500.11797/PC1255
    Autors:
    Montserrat DiéguezOscar PàmiesMARIA BIOSCACarlota Borràs
    Resum:
    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.

  • Altres:

    Autor segons l'article: Montserrat Diéguez Oscar Pàmies MARIA BIOSCA Carlota Borràs
    Departament: Química Física i Inorgànica
    Autor/s de la URV: DIÉGUEZ FERNÁNDEZ, MONTSERRAT PAMIES OLLÉ, OSCAR MARIA BIOSCA BORRÀS NOGUERA, CARLOTA
    Paraules clau: reaction intermediates asymmetric catalysis iridium
    Resum: 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.
    Grup de recerca: Organometàl.lics i Catàlisi Homogènia
    Àrees temàtiques: Chemistry Química Química
    Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 0276-7333
    Identificador de l'autor: 0000-0002-8450-0656 0000-0002-2352-8508 n/a n/a
    Data d'alta del registre: 2015-11-18
    Pàgina final: 5334
    Volum de revista: 34
    Versió de l'article dipositat: info:eu-repo/semantics/acceptedVersion
    Enllaç font original: https://pubs.acs.org/doi/10.1021/acs.organomet.5b00790
    URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
    DOI de l'article: 10.1021/acs.organomet.5b00790
    Entitat: Universitat Rovira i Virgili
    Any de publicació de la revista: 2015
    Pàgina inicial: 5321
    Tipus de publicació: Post-print

  • Paraules clau:

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

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