Articles producció científica> Química Física i Inorgànica

Unlocking the Asymmetric Hydrogenation of Tetrasubstituted Acyclic Enones

  • Datos identificativos

    Identificador: imarina:9332908
    Autores:
    Faiges JBiosca MPericàs MABesora MPàmies ODiéguez M
    Resumen:
    Asymmetric hydrogenation (AH) of tetrasubstituted olefins generating two stereocenters is still an open topic. There are only a few reports on the AH of tetrasubstituted olefins with conjugated functional groups, while this process can create useful intermediates for the subsequent elaboration of relevant end products. Most of the tetrasubstituted olefins successfully submitted to AH belong to a small number of functional classes; remarkably, the AH of tetrasubstituted acyclic enones still represents an unsolved challenge. Herein, we disclose a class of air-stable Ir-P,N catalysts, prepared in three steps from commercially available amino alcohols, that can hydrogenate, in minutes, a wide range of electronically and sterically diverse acyclic tetrasubstituted enones (including exocyclic ones) with high yields and high enantioselectivities. The factors responsible for the excellent selectivities were elucidated by combining deuterogenation experiments and theoretical calculations. The calculations indicated that the reduction follows an IrI/IrIII mechanism, in which enantioselectivity is controlled in the first migratory insertion of the hydride to the most electrophilic olefinic Cβ and the formation of the hydrogenated product via reductive elimination takes place prior to the coordination of dihydrogen and the subsequent oxidative addition. The potential of the new catalytic systems is demonstrated by the derivatization of hydrogenation products.© 2023 Wiley-VCH GmbH.
  • Otros:

    Autor según el artículo: Faiges J; Biosca M; Pericàs MA; Besora M; Pàmies O; Diéguez M
    Departamento: Química Física i Inorgànica
    Autor/es de la URV: Besora Bonet, Maria / Biosca Brull, Maria / Diéguez Fernández, Montserrat / Faiges Marcos, Jorge / Pamies Ollé, Oscar / Pericàs Brondo, Miquel Àngel
    Palabras clave: Theoretical calculations Tetrasubstituted enones Tetrasubsituted olefins N-phosphine-oxazoline Mechanism Iridium catalysts Iridium Enones Asymmetric hydrogenation
    Resumen: Asymmetric hydrogenation (AH) of tetrasubstituted olefins generating two stereocenters is still an open topic. There are only a few reports on the AH of tetrasubstituted olefins with conjugated functional groups, while this process can create useful intermediates for the subsequent elaboration of relevant end products. Most of the tetrasubstituted olefins successfully submitted to AH belong to a small number of functional classes; remarkably, the AH of tetrasubstituted acyclic enones still represents an unsolved challenge. Herein, we disclose a class of air-stable Ir-P,N catalysts, prepared in three steps from commercially available amino alcohols, that can hydrogenate, in minutes, a wide range of electronically and sterically diverse acyclic tetrasubstituted enones (including exocyclic ones) with high yields and high enantioselectivities. The factors responsible for the excellent selectivities were elucidated by combining deuterogenation experiments and theoretical calculations. The calculations indicated that the reduction follows an IrI/IrIII mechanism, in which enantioselectivity is controlled in the first migratory insertion of the hydride to the most electrophilic olefinic Cβ and the formation of the hydrogenated product via reductive elimination takes place prior to the coordination of dihydrogen and the subsequent oxidative addition. The potential of the new catalytic systems is demonstrated by the derivatization of hydrogenation products.© 2023 Wiley-VCH GmbH.
    Áreas temáticas: Química Medicina ii Medicina i Materiais Interdisciplinar General medicine General chemistry Farmacia Engenharias ii Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Astronomia / física
    Direcció de correo del autor: maria.biosca@urv.cat miquelangel.pericas@urv.cat maria.besora@urv.cat jorge.faiges@urv.cat oscar.pamies@urv.cat montserrat.dieguez@urv.cat
    Identificador del autor: 0000-0002-9116-6318 0000-0002-6656-5827 0000-0002-2352-8508 0000-0002-8450-0656
    Fecha de alta del registro: 2024-11-02
    Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
    Enlace a la fuente original: https://onlinelibrary.wiley.com/doi/10.1002/anie.202315872
    URL Documento de licencia: https://repositori.urv.cat/ca/proteccio-de-dades/
    Referencia al articulo segun fuente origial: Angewandte Chemie (International Ed. Print). 63 (9): e202315872-e202315872
    Referencia de l'ítem segons les normes APA: Faiges J; Biosca M; Pericàs MA; Besora M; Pàmies O; Diéguez M (2024). Unlocking the Asymmetric Hydrogenation of Tetrasubstituted Acyclic Enones. Angewandte Chemie (International Ed. Print), 63(9), e202315872-e202315872. DOI: 10.1002/anie.202315872
    DOI del artículo: 10.1002/anie.202315872
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2024
    Tipo de publicación: Journal Publications
  • Palabras clave:

    Catalysis,Chemistry,Chemistry (Miscellaneous),Chemistry, Multidisciplinary
    Theoretical calculations
    Tetrasubstituted enones
    Tetrasubsituted olefins
    N-phosphine-oxazoline
    Mechanism
    Iridium catalysts
    Iridium
    Enones
    Asymmetric hydrogenation
    Química
    Medicina ii
    Medicina i
    Materiais
    Interdisciplinar
    General medicine
    General chemistry
    Farmacia
    Engenharias ii
    Ciências biológicas iii
    Ciências biológicas ii
    Ciências biológicas i
    Chemistry, multidisciplinary
    Chemistry (miscellaneous)
    Chemistry (all)
    Chemistry
    Catalysis
    Astronomia / física
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