Articles producció científica> Química Física i Inorgànica

Third-Generation Amino Acid Furanoside-Based Ligands from d-Mannose for the Asymmetric Transfer Hydrogenation of Ketones: Catalysts with an Exceptionally Wide Substrate Scope

  • Identification data

    Identifier: PC:2535
    Authors:
    Montserrat DiéguezJèssica MargalefTove SlagbrandFredrik TinnisHans AdolfssonOscar Pàmies
    Abstract:
    DOI: 10.1002/adsc.201600903 URL: http://onlinelibrary.wiley.com/doi/10.1002/adsc.201600903/abstract Filiació URV: SI Inclòs a la memòria: SI
  • Others:

    Author, as appears in the article.: Montserrat Diéguez; Jèssica Margalef; Tove Slagbrand; Fredrik Tinnis; Hans Adolfsson; Oscar Pàmies
    Department: Química Física i Inorgànica
    URV's Author/s: DIÉGUEZ FERNÁNDEZ, MONTSERRAT; Jèssica Margalef; Tove Slagbrand; Fredrik Tinnis; Hans Adolfsson; PAMIES OLLÉ, OSCAR
    Keywords: rhodium hydroxyamide ligands asymmetric transfer hydrogenation
    Abstract: A modular ligand library of α-amino acid hydroxyamides and thioamides was prepared from 10 different N-tert-butyloxycarbonyl-protected α-amino acids and three different amino alcohols derived from 2,3-O-isopropylidene-α-d-mannofuranoside. The ligand library was evaluated in the half-sandwich ruthenium- and rhodium-catalyzed asymmetric transfer hydrogenation of a wide array of ketone substrates, including simple as well as sterically demanding aryl alkyl ketones, aryl fluoroalkyl ketones, heteroaromatic alkyl ketones, aliphatic, conjugated and propargylic ketones. Under the optimized reaction conditions, secondary alcohols were obtained in high yields and in enantioselectivities up to >99%. The choice of ligand/catalyst allowed for the generation of both enantiomers of the secondary alcohols, where the ruthenium-hydroxyamide and the rhodium-thioamide catalysts act complementarily towards each other. The catalytic systems were also evaluated in the tandem isomerization/asymmetric transfer hydrogenation of racemic allylic alcohols to yield enantiomerically enriched saturated secondary alcohols in up to 98% ee. Furthermore, the catalytic tandem α-alkylation/asymmetric transfer hydrogenation of acetophenones and 3-acetylpyridine with primary alcohols as alkylating and reducing agents was studied. Secondary alcohols containing an elongated alkyl chain were obtained in up to 92% ee.
    Research group: Organometàl.lics i Catàlisi Homogènia
    Thematic Areas: Chemistry Química Química
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 1615-4169
    Author identifier: 0000-0002-8450-0656; n/a; 0000-0003-2013-8093; 0000-0003-1271-4601; n/a; 0000-0002-2352-8508
    Record's date: 2017-01-18
    Last page: 4018
    Journal volume: 358
    Papper version: info:eu-repo/semantics/acceptedVersion
    Link to the original source: https://onlinelibrary.wiley.com/doi/abs/10.1002/adsc.201600903
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Article's DOI: 10.1002/adsc.201600903
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2016
    First page: 4006
    Publication Type: Post-print
  • Keywords:

    Lligands
    Asimetria (Química)
    Hidrogenació
    rhodium
    hydroxyamide ligands
    asymmetric transfer hydrogenation
    Chemistry
    Química
    Química
    1615-4169
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