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β-Scission by Direct Electrochemical Oxidation: Proton-coupled Electron Transfer Mechanism Dictated by Synthetic Study and Computations (Supporting Information)

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posted on 2023-03-08, 07:19 authored by Rumi IZUMIYA, Mahito Atobe, Naoki SHIDA

 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.

Funding

Development of electrode mediator system using hypervalent compound aimed at green material synthesis

Japan Society for the Promotion of Science

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Iketani Science and Technology Foundation

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Corresponding author email address

shida-naoki-gz@ynu.ac.jp

Copyright

© 2023 The Author(s).

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