Articles producció científica> Química Analítica i Química Orgànica

An Electrocatalytic Cascade Reaction for the Synthesis of Ketones Using CO2 as a CO Surrogate

  • Identification data

    Identifier: imarina:9386368
    Authors:
    Sheta, Ahmed MFernandez, SergioLiu, ChangweiDubed-Bandomo, Geyla CLloret-Fillol, Julio
    Abstract:
    The construction of carbonyl compounds via carbonylation reactions using safe CO sources remains a long-standing challenge to synthetic chemists. Herein, we propose a catalyst cascade Scheme in which CO2 is used as a CO surrogate in the carbonylation of benzyl chlorides. Our approach is based on the cooperation between two coexisting catalytic cycles: the CO2-to-CO electroreduction cycle promoted by [Fe(TPP)Cl] (TPP=meso-tetraphenylporphyrin) and an electrochemical carbonylation cycle catalyzed by [Ni(bpy)Br2] (2,2 '-bipyridine). As a proof of concept, this protocol allows for the synthesis of symmetric ketones from good to excellent yields in an undivided cell with non-sacrificial electrodes. The reaction can be directly scaled up to gram-scale and operates effectively at a CO2 concentration of 10 %, demonstrating its robustness. Our mechanistic studies based on cyclic voltammetry, IR spectroelectrochemistry and Density Functional Theory calculations suggest a synergistic effect between the two catalysts. The CO produced from CO2 reduction is key in the formation of the [Ni(bpy)(CO)2], which is proposed as the catalytic intermediate responsible for the C-C bond formation in the carbonylation steps.
  • Others:

    Author, as appears in the article.: Sheta, Ahmed M; Fernandez, Sergio; Liu, Changwei; Dubed-Bandomo, Geyla C; Lloret-Fillol, Julio
    Department: Química Analítica i Química Orgànica
    URV's Author/s: Fernández Martín, Sergio / Liu, Changwei / Sheta, Ahmed Mohamed Abdelmoaty
    Keywords: Aryl Carbon-monoxide Carbonylation Cascade reaction Co valorization 2 Co2 valorization Coupling reactions Dual catalysi Dual catalysis Electrocatalysis Electrochemical carboxylation Electroreductive alkylation Iron(ii) porphyrins Nickel-catalyzed electrosynthesis Organic halides Reductio
    Abstract: The construction of carbonyl compounds via carbonylation reactions using safe CO sources remains a long-standing challenge to synthetic chemists. Herein, we propose a catalyst cascade Scheme in which CO2 is used as a CO surrogate in the carbonylation of benzyl chlorides. Our approach is based on the cooperation between two coexisting catalytic cycles: the CO2-to-CO electroreduction cycle promoted by [Fe(TPP)Cl] (TPP=meso-tetraphenylporphyrin) and an electrochemical carbonylation cycle catalyzed by [Ni(bpy)Br2] (2,2 '-bipyridine). As a proof of concept, this protocol allows for the synthesis of symmetric ketones from good to excellent yields in an undivided cell with non-sacrificial electrodes. The reaction can be directly scaled up to gram-scale and operates effectively at a CO2 concentration of 10 %, demonstrating its robustness. Our mechanistic studies based on cyclic voltammetry, IR spectroelectrochemistry and Density Functional Theory calculations suggest a synergistic effect between the two catalysts. The CO produced from CO2 reduction is key in the formation of the [Ni(bpy)(CO)2], which is proposed as the catalytic intermediate responsible for the C-C bond formation in the carbonylation steps.
    Thematic Areas: Astronomia / física Catalysis Chemistry Chemistry (all) Chemistry (miscellaneous) Chemistry, multidisciplinary Ciências biológicas i Ciências biológicas ii Ciências biológicas iii Engenharias ii Farmacia General chemistry General medicine Interdisciplinar Materiais Medicina i Medicina ii Química
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    Author's mail: sergio.fernandezm@estudiants.urv.cat ahmedmohamedabdelmoaty.sheta@estudiants.urv.cat changwei.liu@estudiants.urv.cat
    Author identifier: 0000-0002-9389-6349
    Record's date: 2024-10-12
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202403674
    Papper original source: Angewandte Chemie (International Ed. Print). 63 (23): e202403674-
    APA: Sheta, Ahmed M; Fernandez, Sergio; Liu, Changwei; Dubed-Bandomo, Geyla C; Lloret-Fillol, Julio (2024). An Electrocatalytic Cascade Reaction for the Synthesis of Ketones Using CO2 as a CO Surrogate. Angewandte Chemie (International Ed. Print), 63(23), e202403674-. DOI: 10.1002/anie.202403674
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Article's DOI: 10.1002/anie.202403674
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2024
    Publication Type: Journal Publications
  • Keywords:

    Catalysis,Chemistry,Chemistry (Miscellaneous),Chemistry, Multidisciplinary
    Aryl
    Carbon-monoxide
    Carbonylation
    Cascade reaction
    Co valorization 2
    Co2 valorization
    Coupling reactions
    Dual catalysi
    Dual catalysis
    Electrocatalysis
    Electrochemical carboxylation
    Electroreductive alkylation
    Iron(ii) porphyrins
    Nickel-catalyzed electrosynthesis
    Organic halides
    Reductio
    Astronomia / física
    Catalysis
    Chemistry
    Chemistry (all)
    Chemistry (miscellaneous)
    Chemistry, multidisciplinary
    Ciências biológicas i
    Ciências biológicas ii
    Ciências biológicas iii
    Engenharias ii
    Farmacia
    General chemistry
    General medicine
    Interdisciplinar
    Materiais
    Medicina i
    Medicina ii
    Química
  • Documents:

  • Cerca a google

    Search to google scholar