Articles producció científica> Química Física i Inorgànica

Chiral 1-Phosphabarrelene-Pyridines as Suitable Ligands for the Rh/Ir-Catalyzed Asymmetric Hydrogenation of Olefins

  • Identification data

    Identifier: imarina:9333967
    Authors:
    Saltó, JTarr, DPetrov, AReich, DWeber, MBiosca, MPamies, OMüller, CDiéguez, M
    Abstract:
    Herein, we report the synthesis of chiral phosphabarrelene-pyridine ligands. Their synthesis benefit from modified reaction conditions to overcome the low yields normally associated with the [4+2] cycloaddition reaction of phosphinines with hexafluoro-2-butyne, which is a key to install the P-stereocenter in the phosphabarrelene. Their potential as chelating ligands in asymmetric catalysis was assessed in the Rh- and Ir-catalyzed hydrogenation of cyclic β-enamides and β-dehydroamino acid derivatives. The catalytic system containing a tert-butyl substituent at the ortho position of the phosphabarrelene moiety successfully hydrogenates a range of cyclic β-enamides (ee's between 92% to 94%) and β-dehydroamino acid derivatives (ee's between 93% to 95%). Moreover, the reactions can be carried out in the environmentally friendly 1,2-propylene carbonate as solvent with no loss of enantioselectivity. Mechanistic studies with the Rh/P,N catalytic systems agree with the Landis-Halpern mechanism and explain the influence of the substituent at the phosphabarrelene on enantioselectivity. Finally, the hydrogenation reactions can be carried out at large scale maintaining high enantioselectivities.
  • Others:

    Author, as appears in the article.: Saltó, J; Tarr, D; Petrov, A; Reich, D; Weber, M; Biosca, M; Pamies, O; Müller, C; Diéguez, M
    Department: Química Física i Inorgànica
    URV's Author/s: Biosca Brull, Maria / Diéguez Fernández, Montserrat / Pamies Ollé, Oscar
    Keywords: Phosphabarrelene Oxazoline-containing ligands Olefins Mechanistic insights Bidentate p,n ligands Asymmetric hydrogenation rh olefins mechanistic insights mechanism evolution cyclic beta-enamides complexes bidentate p,n ligands asymmetric hydrogenation amino-acid-derivatives activation
    Abstract: Herein, we report the synthesis of chiral phosphabarrelene-pyridine ligands. Their synthesis benefit from modified reaction conditions to overcome the low yields normally associated with the [4+2] cycloaddition reaction of phosphinines with hexafluoro-2-butyne, which is a key to install the P-stereocenter in the phosphabarrelene. Their potential as chelating ligands in asymmetric catalysis was assessed in the Rh- and Ir-catalyzed hydrogenation of cyclic β-enamides and β-dehydroamino acid derivatives. The catalytic system containing a tert-butyl substituent at the ortho position of the phosphabarrelene moiety successfully hydrogenates a range of cyclic β-enamides (ee's between 92% to 94%) and β-dehydroamino acid derivatives (ee's between 93% to 95%). Moreover, the reactions can be carried out in the environmentally friendly 1,2-propylene carbonate as solvent with no loss of enantioselectivity. Mechanistic studies with the Rh/P,N catalytic systems agree with the Landis-Halpern mechanism and explain the influence of the substituent at the phosphabarrelene on enantioselectivity. Finally, the hydrogenation reactions can be carried out at large scale maintaining high enantioselectivities.
    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/
    Author's mail: maria.biosca@urv.cat montserrat.dieguez@urv.cat oscar.pamies@urv.cat
    Author identifier: 0000-0002-9116-6318 0000-0002-8450-0656 0000-0002-2352-8508
    Record's date: 2024-05-11
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://onlinelibrary.wiley.com/doi/full/10.1002/adsc.202301358
    Papper original source: Advanced Synthesis & Catalysis. 366 (4): 813-821
    APA: Saltó, J; Tarr, D; Petrov, A; Reich, D; Weber, M; Biosca, M; Pamies, O; Müller, C; Diéguez, M (2024). Chiral 1-Phosphabarrelene-Pyridines as Suitable Ligands for the Rh/Ir-Catalyzed Asymmetric Hydrogenation of Olefins. Advanced Synthesis & Catalysis, 366(4), 813-821. DOI: 10.1002/adsc.202301358
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Article's DOI: 10.1002/adsc.202301358
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2024
    Publication Type: Journal Publications
  • Keywords:

    Catalysis,Chemistry, Applied,Chemistry, Organic,Organic Chemistry
    Phosphabarrelene
    Oxazoline-containing ligands
    Olefins
    Mechanistic insights
    Bidentate p,n ligands
    Asymmetric hydrogenation
    rh
    olefins
    mechanistic insights
    mechanism
    evolution
    cyclic beta-enamides
    complexes
    bidentate p,n ligands
    asymmetric hydrogenation
    amino-acid-derivatives
    activation
    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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