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

  • Identification data

    Identifier: imarina:9230635
    Authors:
    Faiges JBorràs CPastor IMPàmies OBesora MDiéguez M
    Abstract:
    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%).
  • Others:

    Author, as appears in the article.: Faiges J; Borràs C; Pastor IM; Pàmies O; Besora M; Diéguez M
    Department: Química Física i Inorgànica
    URV's Author/s: Besora Bonet, Maria / BORRÀS NOGUERA, CARLOTA / Diéguez Fernández, Montserrat / Faiges Marcos, Jorge / Pamies Ollé, Oscar / Pastor Gosálbez, María Inmaculada
    Keywords: 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
    Abstract: 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%).
    Thematic Areas: 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
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    Author's mail: maria.besora@urv.cat jorge.faiges@urv.cat oscar.pamies@urv.cat montserrat.dieguez@urv.cat inma.pastor@urv.cat
    Author identifier: 0000-0002-6656-5827 0000-0002-2352-8508 0000-0002-8450-0656 0000-0003-4913-0722
    Record's date: 2024-07-27
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://pubs.acs.org/doi/10.1021/acs.organomet.1c00450
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Organometallics. 40 (20): 3424-3435
    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
    Article's DOI: 10.1021/acs.organomet.1c00450
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2021
    Publication Type: Journal Publications
  • Keywords:

    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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