An Electrocatalytic Cascade Reaction for the Synthesis of Ketones Using CO2 as a CO Surrogate
© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH..
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.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2024 |
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| Erschienen: |
2024 |
| Enthalten in: |
Zur Gesamtaufnahme - year:2024 |
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| Enthalten in: |
Angewandte Chemie (International ed. in English) - (2024) vom: 22. Apr., Seite e202403674 |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Sheta, Ahmed M [VerfasserIn] |
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| Links: |
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| Themen: |
CO2 valorization |
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| Anmerkungen: |
Date Revised 22.04.2024 published: Print-Electronic Citation Status Publisher |
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| doi: |
10.1002/anie.202403674 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM371363144 |
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| 245 | 1 | 3 | |a An Electrocatalytic Cascade Reaction for the Synthesis of Ketones Using CO2 as a CO Surrogate |
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| 520 | |a © 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH. | ||
| 520 | |a 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 | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a CO2 valorization | |
| 650 | 4 | |a Electrocatalysis | |
| 650 | 4 | |a carbonylation | |
| 650 | 4 | |a cascade reaction | |
| 650 | 4 | |a dual catalysis | |
| 700 | 1 | |a Fernández, Sergio |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Changwei |e verfasserin |4 aut | |
| 700 | 1 | |a Dubed-Bandomo, Geyla C |e verfasserin |4 aut | |
| 700 | 1 | |a Lloret-Fillol, Julio |e verfasserin |4 aut | |
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| 856 | 4 | 0 | |u http://dx.doi.org/10.1002/anie.202403674 |3 Volltext |
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