Articles producció científica> Química Física i Inorgànica

Understanding the mechanism of transition metal-free: Anti addition to alkynes: The selenoboration case

  • Datos identificativos

    Identificador: imarina:6389464
    Handle: http://hdl.handle.net/20.500.11797/imarina6389464
  • Autores:

    García-López D
    Civit MG
    Vogels CM
    Ricart JM
    Westcott SA
    Fernández E
    Carbó JJ
  • Otros:

    Autor según el artículo: García-López D; Civit MG; Vogels CM; Ricart JM; Westcott SA; Fernández E; Carbó JJ
    Departamento: Química Física i Inorgànica
    Autor/es de la URV: Carbó Martin, Jorge Juan / Fernández Gutiérrez, Maria Elena / GARCIA CIVIT, MARC / Ricart Pla, Jose Manuel
    Palabras clave: Stereoselective anti-addition Selenoboration
    Resumen: © 2018 The Royal Society of Chemistry. The stereoselective anti-addition of selenoboranes to α,β-acetylenic esters and amides was achieved in a transition metal-free context using catalytic amounts of PCy3. The reaction provides anti-3,4-selenoboration with concomitant delivery of α-vinyl selenides by protodeboronation with MeOH. Interestingly, in the absence of phosphine the selenoboration switches towards the formation of β-vinyl selenides. Theoretical calculations rationalize the regio- and stereoselectivity of the reaction by discovering a new mechanism for the anti-3,4-selenoboration. While the selenoborane is activated via the push-pull effect of B, the phosphine interacts with the β position of the alkynoate switching the polarity of the triple bond and favoring 1,3-selenoboration which provides the α-addition of the selenyl group. Then, the autocatalytic action of a second selenoborane reagent, which coordinates to the phosphorus ylide intermediate, determines the stereoselectivity and completes the catalytic process. Finally, the comparison of selenoborane reagents with diboranes and silaboranes, which have exhibited analogous reactivity, shows that the selenium moiety has a larger nucleophilic character favoring the performance of the reaction under mild conditions.
    Áreas temáticas: Química Materiais Farmacia Engenharias ii Engenharias i Ciências biológicas ii Ciências biológicas i Ciências agrárias i Ciência de alimentos Chemistry, physical Catalysis Biotecnología Astronomia / física
    Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/
    ISSN: 20444753
    Direcció de correo del autor: mariaelena.fernandez@urv.cat josep.ricart@urv.cat j.carbo@urv.cat
    Identificador del autor: 0000-0001-9025-1791 0000-0002-2610-5535 0000-0002-3945-6721
    Fecha de alta del registro: 2023-02-26
    Versión del articulo depositado: info:eu-repo/semantics/publishedVersion
    Enlace a la fuente original: https://pubs.rsc.org/en/content/articlelanding/2018/cy/c7cy02295f#!divAbstract
    URL Documento de licencia: http://repositori.urv.cat/ca/proteccio-de-dades/
    Referencia al articulo segun fuente origial: Catalysis Science & Technology. 8 (14): 3617-3628
    Referencia de l'ítem segons les normes APA: García-López D; Civit MG; Vogels CM; Ricart JM; Westcott SA; Fernández E; Carbó JJ (2018). Understanding the mechanism of transition metal-free: Anti addition to alkynes: The selenoboration case. Catalysis Science & Technology, 8(14), 3617-3628. DOI: 10.1039/c7cy02295f
    DOI del artículo: 10.1039/c7cy02295f
    Entidad: Universitat Rovira i Virgili
    Año de publicación de la revista: 2018
    Tipo de publicación: Journal Publications
  • Palabras clave:

    Catalysis,Chemistry, Physical
    Stereoselective anti-addition
    Selenoboration
    Química
    Materiais
    Farmacia
    Engenharias ii
    Engenharias i
    Ciências biológicas ii
    Ciências biológicas i
    Ciências agrárias i
    Ciência de alimentos
    Chemistry, physical
    Catalysis
    Biotecnología
    Astronomia / física
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