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Density Functional Theory-Inspired Design of Ir/P,S-Catalysts for Asymmetric Hydrogenation of Olefins

  • Datos identificativos

    Identificador: imarina:9230635
    Autores:
    Faiges JBorràs CPastor IMPàmies OBesora MDiéguez M
    Resumen:
    In silico-based optimization of Ir/P,S-catalysts for the asymmetric hydrogenation of unfunctionalized olefins using (E)-1-(but-2-en-2-yl)-4-methoxybenzene as a benchmark olefin has been carried out. DFT calculations revealed that the thioether group has a major role in directing the olefin coordination. This, together with the configuration of the biphenyl phosphite group, has an impact in maximizing the energy gap between the most stable transition states leading to opposite enantiomers. As a result, the optimized catalyst proved to be efficient in the hydrogenation of a range of alkenes with the same substitution pattern and olefin geometry as the benchmark olefin, regardless of the presence of functional groups with different coordination abilities (ee values up to 97%). Appealingly, further modifications at the thioether groups and at the biaryl phosphite moiety allowed the highly enantioselective hydrogenation of olefins with different substitution patterns (e.g., α,β-unsaturated lactones and lactams, 1,1′-disubstituted enol phosphinates, and cyclic β-enamides; ee values up to >99%).
  • Otros:

    Autor según el artículo: Faiges J; Borràs C; Pastor IM; Pàmies O; Besora M; Diéguez M
    Departamento: Química Física i Inorgànica
    Autor/es de la URV: Besora Bonet, Maria / BORRÀS NOGUERA, CARLOTA / Diéguez Fernández, Montserrat / Faiges Marcos, Jorge / Pamies Ollé, Oscar / Pastor Gosálbez, María Inmaculada
    Palabras clave: Iridium-catalyzed hydrogenation selective catalysts phosphite-oxazoline ligands molecular-orbital methods mechanistic insights highly enantioselective hydrogenation gaussian-type basis effective core potentials cyclic beta-enamides basis-sets
    Resumen: In silico-based optimization of Ir/P,S-catalysts for the asymmetric hydrogenation of unfunctionalized olefins using (E)-1-(but-2-en-2-yl)-4-methoxybenzene as a benchmark olefin has been carried out. DFT calculations revealed that the thioether group has a major role in directing the olefin coordination. This, together with the configuration of the biphenyl phosphite group, has an impact in maximizing the energy gap between the most stable transition states leading to opposite enantiomers. As a result, the optimized catalyst proved to be efficient in the hydrogenation of a range of alkenes with the same substitution pattern and olefin geometry as the benchmark olefin, regardless of the presence of functional groups with different coordination abilities (ee values up to 97%). Appealingly, further modifications at the thioether groups and at the biaryl phosphite moiety allowed the highly enantioselective hydrogenation of olefins with different substitution patterns (e.g., α,β-unsaturated lactones and lactams, 1,1′-disubstituted enol phosphinates, and cyclic β-enamides; ee values up to >99%).
    Áreas temáticas: Química Physical and theoretical chemistry Organic chemistry Materiais Inorganic chemistry Engenharias ii Ciências biológicas ii Ciências agrárias i Chemistry, organic Chemistry, inorganic & nuclear Astronomia / física
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    Direcció de correo del autor: maria.besora@urv.cat jorge.faiges@urv.cat oscar.pamies@urv.cat montserrat.dieguez@urv.cat inma.pastor@urv.cat
    Identificador del autor: 0000-0002-6656-5827 0000-0002-2352-8508 0000-0002-8450-0656 0000-0003-4913-0722
    Fecha de alta del registro: 2024-07-27
    Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
    Enlace a la fuente original: https://pubs.acs.org/doi/10.1021/acs.organomet.1c00450
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referencia al articulo segun fuente origial: Organometallics. 40 (20): 3424-3435
    Referencia de l'ítem segons les normes APA: Faiges J; Borràs C; Pastor IM; Pàmies O; Besora M; Diéguez M (2021). Density Functional Theory-Inspired Design of Ir/P,S-Catalysts for Asymmetric Hydrogenation of Olefins. Organometallics, 40(20), 3424-3435. DOI: 10.1021/acs.organomet.1c00450
    DOI del artículo: 10.1021/acs.organomet.1c00450
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2021
    Tipo de publicación: Journal Publications
  • Palabras clave:

    Chemistry, Inorganic & Nuclear,Chemistry, Organic,Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry
    Iridium-catalyzed hydrogenation
    selective catalysts
    phosphite-oxazoline ligands
    molecular-orbital methods
    mechanistic insights
    highly enantioselective hydrogenation
    gaussian-type basis
    effective core potentials
    cyclic beta-enamides
    basis-sets
    Química
    Physical and theoretical chemistry
    Organic chemistry
    Materiais
    Inorganic chemistry
    Engenharias ii
    Ciências biológicas ii
    Ciências agrárias i
    Chemistry, organic
    Chemistry, inorganic & nuclear
    Astronomia / física
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