β-Scission by Direct Electrochemical Oxidation: Proton-coupled Electron Transfer Mechanism Dictated by Synthetic Study and Computations
β-Scission from alkoxy radical enables selective Csp3-Csp3 bond cleavage under ambient conditions, offering a useful method for organic synthesis. Various photocatalytic systems for β-scission have been reported, where proton-coupled electron transfer (PCET) mechanism plays a key role in the generat...
| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
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The Electrochemical Society of Japan
2023-11-01
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| Series: | Electrochemistry |
| Subjects: | |
| Online Access: | https://www.jstage.jst.go.jp/article/electrochemistry/91/11/91_23-67010/_html/-char/en |
| _version_ | 1797447916602785792 |
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| author | Rumi IZUMIYA Mahito ATOBE Naoki SHIDA |
| author_facet | Rumi IZUMIYA Mahito ATOBE Naoki SHIDA |
| author_sort | Rumi IZUMIYA |
| collection | DOAJ |
| description | β-Scission from alkoxy radical enables selective Csp3-Csp3 bond cleavage under ambient conditions, offering a useful method for organic synthesis. Various photocatalytic systems for β-scission have been reported, where proton-coupled electron transfer (PCET) mechanism plays a key role in the generation of alkoxy radical and thus β-scission. Electrochemical β-scission has been mainly pioneered in the presence of mediator, and a direct electrochemical system has rarely been investigated. Here, we investigated the β-scission via direct electrochemical oxidation using a model compound with β-O-4 linkage. Synthetic experiments suggested smooth progress of β-scission in the presence of collidine as a base. Cyclic voltammetry measurement, voltammetric simulation, and quantum simulation suggested the PCET mechanism is responsible for the electrochemical reaction, which is followed by β-scission process. This report provides fundamental insights into the electrochemical β-scission via direct electron transfer on the electrode, which contribute to future applications such as biomass valorization. |
| first_indexed | 2024-03-09T14:02:51Z |
| format | Article |
| id | doaj.art-50288f0d6ee9483faa17142c4a675b97 |
| institution | Directory Open Access Journal |
| issn | 2186-2451 |
| language | English |
| last_indexed | 2024-03-09T14:02:51Z |
| publishDate | 2023-11-01 |
| publisher | The Electrochemical Society of Japan |
| record_format | Article |
| series | Electrochemistry |
| spelling | doaj.art-50288f0d6ee9483faa17142c4a675b972023-11-30T06:15:00ZengThe Electrochemical Society of JapanElectrochemistry2186-24512023-11-01911111200311200310.5796/electrochemistry.23-67010electrochemistryβ-Scission by Direct Electrochemical Oxidation: Proton-coupled Electron Transfer Mechanism Dictated by Synthetic Study and ComputationsRumi IZUMIYA0Mahito ATOBE1https://orcid.org/0000-0002-3173-3608Naoki SHIDA2https://orcid.org/0000-0003-0586-1216Graduate School of Science and Engineering, Yokohama National UniversityGraduate School of Science and Engineering, Yokohama National UniversityGraduate School of Science and Engineering, Yokohama National Universityβ-Scission from alkoxy radical enables selective Csp3-Csp3 bond cleavage under ambient conditions, offering a useful method for organic synthesis. Various photocatalytic systems for β-scission have been reported, where proton-coupled electron transfer (PCET) mechanism plays a key role in the generation of alkoxy radical and thus β-scission. Electrochemical β-scission has been mainly pioneered in the presence of mediator, and a direct electrochemical system has rarely been investigated. Here, we investigated the β-scission via direct electrochemical oxidation using a model compound with β-O-4 linkage. Synthetic experiments suggested smooth progress of β-scission in the presence of collidine as a base. Cyclic voltammetry measurement, voltammetric simulation, and quantum simulation suggested the PCET mechanism is responsible for the electrochemical reaction, which is followed by β-scission process. This report provides fundamental insights into the electrochemical β-scission via direct electron transfer on the electrode, which contribute to future applications such as biomass valorization.https://www.jstage.jst.go.jp/article/electrochemistry/91/11/91_23-67010/_html/-char/enβ-scissioncsp3-csp3 bond cleavageelectrochemical proton-coupled electron transfercyclic voltammetry simulation |
| spellingShingle | Rumi IZUMIYA Mahito ATOBE Naoki SHIDA β-Scission by Direct Electrochemical Oxidation: Proton-coupled Electron Transfer Mechanism Dictated by Synthetic Study and Computations Electrochemistry β-scission csp3-csp3 bond cleavage electrochemical proton-coupled electron transfer cyclic voltammetry simulation |
| title | β-Scission by Direct Electrochemical Oxidation: Proton-coupled Electron Transfer Mechanism Dictated by Synthetic Study and Computations |
| title_full | β-Scission by Direct Electrochemical Oxidation: Proton-coupled Electron Transfer Mechanism Dictated by Synthetic Study and Computations |
| title_fullStr | β-Scission by Direct Electrochemical Oxidation: Proton-coupled Electron Transfer Mechanism Dictated by Synthetic Study and Computations |
| title_full_unstemmed | β-Scission by Direct Electrochemical Oxidation: Proton-coupled Electron Transfer Mechanism Dictated by Synthetic Study and Computations |
| title_short | β-Scission by Direct Electrochemical Oxidation: Proton-coupled Electron Transfer Mechanism Dictated by Synthetic Study and Computations |
| title_sort | β scission by direct electrochemical oxidation proton coupled electron transfer mechanism dictated by synthetic study and computations |
| topic | β-scission csp3-csp3 bond cleavage electrochemical proton-coupled electron transfer cyclic voltammetry simulation |
| url | https://www.jstage.jst.go.jp/article/electrochemistry/91/11/91_23-67010/_html/-char/en |
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