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Synthesis, Application and Kinetic Studies of Chiral Phosphite-Oxazoline Palladium Complexes as Active and Selective Catalysts in Intermolecular Heck Reactions

  • Identification data

    Identifier: imarina:4123828
    Authors:
    Mazloomi ZMagre MDel Valle EPericàs MAPàmies Ovan Leeuwen PWNMDiéguez M
    Abstract:
    © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim This study identifies new phosphite-oxazoline ligands that have been successfully applied in the palladium-catalyzed intermolecular asymmetric Heck reaction. The design of the new phosphite-oxazoline ligands derives from a previous successful generation of phosphine-oxazoline ligands, by replacing the phosphine group with several π-acceptor biaryl phosphite moieties. With these simple modifications, the new phosphite-based ligands, unlike previous phosphine-oxazoline, not only present a modular design with numerous potential phosphite groups available, but they are also air-stable solids, which can be made in the same number of synthetic steps as the phosphine analogues. The substitution of the phosphine by a biaryl phosphite group extended the range of substrates and triflates sources that can be coupled with regio-, enantioselectivities and activities comparable to the few best ones reported. In addition, the ligands that provided the best selectivities contained an isopropyl oxazoline moiety instead of the tert-butyl group found in the related phosphine-oxazoline ligands, which is made from a much more expensive precursor. In this paper we have also carried out kinetic studies and a Hammett plot analysis to determine the rate determining step of this system in the regime of interest. We suggest a likely explanation for the fast Heck reaction of the phosphite-oxazoline catalysts. (Figure presented.).
  • Others:

    Author, as appears in the article.: Mazloomi Z; Magre M; Del Valle E; Pericàs MA; Pàmies O; van Leeuwen PWNM; Diéguez M
    Department: Química Física i Inorgànica
    URV's Author/s: Diéguez Fernández, Montserrat / Pamies Ollé, Oscar
    Keywords: Palladium P,n-ligands Kinetic study Intermolecular heck reaction Asymmetric catalysis
    Abstract: © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim This study identifies new phosphite-oxazoline ligands that have been successfully applied in the palladium-catalyzed intermolecular asymmetric Heck reaction. The design of the new phosphite-oxazoline ligands derives from a previous successful generation of phosphine-oxazoline ligands, by replacing the phosphine group with several π-acceptor biaryl phosphite moieties. With these simple modifications, the new phosphite-based ligands, unlike previous phosphine-oxazoline, not only present a modular design with numerous potential phosphite groups available, but they are also air-stable solids, which can be made in the same number of synthetic steps as the phosphine analogues. The substitution of the phosphine by a biaryl phosphite group extended the range of substrates and triflates sources that can be coupled with regio-, enantioselectivities and activities comparable to the few best ones reported. In addition, the ligands that provided the best selectivities contained an isopropyl oxazoline moiety instead of the tert-butyl group found in the related phosphine-oxazoline ligands, which is made from a much more expensive precursor. In this paper we have also carried out kinetic studies and a Hammett plot analysis to determine the rate determining step of this system in the regime of interest. We suggest a likely explanation for the fast Heck reaction of the phosphite-oxazoline catalysts. (Figure presented.).
    Thematic Areas: Química Organic chemistry Materiais Engenharias iv Engenharias ii Ciências biológicas ii Ciência de alimentos Chemistry, organic Chemistry, applied Catalysis Biodiversidade Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 1615-4150
    Author's mail: oscar.pamies@urv.cat montserrat.dieguez@urv.cat
    Author identifier: 0000-0002-2352-8508 0000-0002-8450-0656
    Record's date: 2024-09-07
    Journal volume: 360
    Papper version: info:eu-repo/semantics/acceptedVersion
    Link to the original source: https://onlinelibrary.wiley.com/doi/abs/10.1002/adsc.201701603
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Advanced Synthesis & Catalysis. 360 (8): 1650-1664
    APA: Mazloomi Z; Magre M; Del Valle E; Pericàs MA; Pàmies O; van Leeuwen PWNM; Diéguez M (2018). Synthesis, Application and Kinetic Studies of Chiral Phosphite-Oxazoline Palladium Complexes as Active and Selective Catalysts in Intermolecular Heck Reactions. Advanced Synthesis & Catalysis, 360(8), 1650-1664. DOI: 10.1002/adsc.201701603
    Article's DOI: 10.1002/adsc.201701603
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2018
    Publication Type: Journal Publications
  • Keywords:

    Catalysis,Chemistry, Applied,Chemistry, Organic,Organic Chemistry
    Palladium
    P,n-ligands
    Kinetic study
    Intermolecular heck reaction
    Asymmetric catalysis
    Química
    Organic chemistry
    Materiais
    Engenharias iv
    Engenharias ii
    Ciências biológicas ii
    Ciência de alimentos
    Chemistry, organic
    Chemistry, applied
    Catalysis
    Biodiversidade
    Astronomia / física
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