Articles producció científica> Química Física i Inorgànica

An improved class of phosphite-oxazoline ligands for Pd-catalyzed allylic substitution reactions

  • Identification data

    Identifier: imarina:5874117
    Authors:
    Biosca MSalto JMagre MNorrby PPamies ODieguez M
    Abstract:
    © 2019 American Chemical Society. A method for generation of Pd/phosphite-oxazoline catalysts containing an alkyl backbone chain has been successfully applied to Pd-catalyzed allylic substitution reactions. By carefully selecting the substituents at both the alkyl backbone chain and the oxazoline of the ligand, as well as the configuration of the biaryl phosphite group, high activities (TOF > 8000 mol substrate × (mol Pd × h)−1) and excellent enantioselectivities (ee's up to 99%) have been achieved for many hindered and unhindered substrates with a wide range of C-, O-, and N-nucleophiles (73 substitution products in total). Moreover, DFT and NMR studies of the key Pd-allyl complexes allowed us to better understand the origin of the excellent enantioselectivities observed experimentally. The useful application of the Pd/phosphite-oxazoline catalysts was demonstrated by the syntheses of many chiral carbobicycles, with multiples stereocenters, by simple sequential reactions involving Pd-allylic substitution and either 1,6-enyne cyclization or Pauson−Khand enyne cyclization.
  • Others:

    Author, as appears in the article.: Biosca M; Salto J; Magre M; Norrby P; Pamies O; Dieguez M
    Department: Química Física i Inorgànica
    URV's Author/s: Biosca Brull, Maria / Diéguez Fernández, Montserrat / Pamies Ollé, Oscar / Saltó De La Torre, Joan
    Keywords: Palladium Nmr study N-ligands Molecular-orbital methods Modular ligands Mixed p,n-ligands Mixed p Kinetic resolution Force-field parameters Enantioselective allylation Dft calculations Cyclobutane backbone Basis-sets Asymmetric-synthesis Asymmetric allylic substitution Alkylation Ab-initio
    Abstract: © 2019 American Chemical Society. A method for generation of Pd/phosphite-oxazoline catalysts containing an alkyl backbone chain has been successfully applied to Pd-catalyzed allylic substitution reactions. By carefully selecting the substituents at both the alkyl backbone chain and the oxazoline of the ligand, as well as the configuration of the biaryl phosphite group, high activities (TOF > 8000 mol substrate × (mol Pd × h)−1) and excellent enantioselectivities (ee's up to 99%) have been achieved for many hindered and unhindered substrates with a wide range of C-, O-, and N-nucleophiles (73 substitution products in total). Moreover, DFT and NMR studies of the key Pd-allyl complexes allowed us to better understand the origin of the excellent enantioselectivities observed experimentally. The useful application of the Pd/phosphite-oxazoline catalysts was demonstrated by the syntheses of many chiral carbobicycles, with multiples stereocenters, by simple sequential reactions involving Pd-allylic substitution and either 1,6-enyne cyclization or Pauson−Khand enyne cyclization.
    Thematic Areas: Química Materiais Interdisciplinar General chemistry Engenharias ii Ciências agrárias i Chemistry, physical Chemistry (miscellaneous) Chemistry (all) Catalysis Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 21555435
    Author's mail: maria.biosca@urv.cat montserrat.dieguez@urv.cat oscar.pamies@urv.cat joan.salto@estudiants.urv.cat joan.salto@estudiants.urv.cat
    Author identifier: 0000-0002-9116-6318 0000-0002-8450-0656 0000-0002-2352-8508 0000-0003-4846-8473 0000-0003-4846-8473
    Last page: 6048
    Record's date: 2023-12-16
    Journal volume: 9
    Papper version: info:eu-repo/semantics/submittedVersion
    Link to the original source: https://pubs.acs.org/doi/10.1021/acscatal.9b01166
    Papper original source: Acs Catalysis. 9 (7): 6033-6048
    APA: Biosca M; Salto J; Magre M; Norrby P; Pamies O; Dieguez M (2019). An improved class of phosphite-oxazoline ligands for Pd-catalyzed allylic substitution reactions. Acs Catalysis, 9(7), 6033-6048. DOI: 10.1021/acscatal.9b01166
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Article's DOI: 10.1021/acscatal.9b01166
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2019
    First page: 6033
    Publication Type: Journal Publications
  • Keywords:

    Catalysis,Chemistry (Miscellaneous),Chemistry, Physical
    Palladium
    Nmr study
    N-ligands
    Molecular-orbital methods
    Modular ligands
    Mixed p,n-ligands
    Mixed p
    Kinetic resolution
    Force-field parameters
    Enantioselective allylation
    Dft calculations
    Cyclobutane backbone
    Basis-sets
    Asymmetric-synthesis
    Asymmetric allylic substitution
    Alkylation
    Ab-initio
    Química
    Materiais
    Interdisciplinar
    General chemistry
    Engenharias ii
    Ciências agrárias i
    Chemistry, physical
    Chemistry (miscellaneous)
    Chemistry (all)
    Catalysis
    Astronomia / física
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