Solvent-directed Cathodic Deoxygenation of Carbonyl Compounds and Alcohols
Abstract
The deoxygenation of carbonyl compounds and alcohols is an important transformation in organic chemistry but remains challenging with respect to selectivity and resource efficiency. Herein, we present a metal-free electroreductive method for deoxygenation of both compound classes, which involves simple means (undivided cell, galvanostatic conditions) and covers a broad range of substrates in which the carbonyl/hydroxyl groups are each located in benzylic position. Key to success is the use of dimethyl carbonate (DMC) as a solvent, which promotes the formation of readily reducible methyl carbonate intermediates from the respective electrochemically inert alcohols. The in situ-formed methyl carbonate group thus plays a dual role, first as an electro-auxiliary supporting the accommodation of negative charge upon cathodic reduction, and then as efficient leaving group to facilitate formation of carbon-centered radical intermediates. In addition to a comprehensive investigation of the scope of alcohol and carbonyl substrates, including scale-up to the gram level, our work also includes a detailed mechanistic analysis based on cyclic voltammetry, control experiments, and quantum chemical calculations. The study illustrates how electrolyte engineering can be effectively used for steering the selectivity in electro-organic synthesis.
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BibTeX
@misc{zeng2026solventdirected,
title = {{Solvent-directed Cathodic Deoxygenation of Carbonyl Compounds and Alcohols}},
author = {He Zeng and Zahra Tayebi and Anton Scherkus and Bernd H. Müller and Olga S. Bokareva and Robert Francke},
howpublished = {ChemRxiv},
year = {2026},
month = aug,
doi = {10.26434/chemrxiv.15008072/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008072/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Solvent-directed Cathodic Deoxygenation of Carbonyl Compounds and Alcohols
AU - He Zeng
AU - Zahra Tayebi
AU - Anton Scherkus
AU - Bernd H. Müller
AU - Olga S. Bokareva
AU - Robert Francke
PY - 2026
DA - 2026/08/31
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008072/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008072/v1
AB - The deoxygenation of carbonyl compounds and alcohols is an important transformation in organic chemistry but remains challenging with respect to selectivity and resource efficiency. Herein, we present a metal-free electroreductive method for deoxygenation of both compound classes, which involves simple means (undivided cell, galvanostatic conditions) and covers a broad range of substrates in which the carbonyl/hydroxyl groups are each located in benzylic position. Key to success is the use of dimethyl carbonate (DMC) as a solvent, which promotes the formation of readily reducible methyl carbonate intermediates from the respective electrochemically inert alcohols. The in situ-formed methyl carbonate group thus plays a dual role, first as an electro-auxiliary supporting the accommodation of negative charge upon cathodic reduction, and then as efficient leaving group to facilitate formation of carbon-centered radical intermediates. In addition to a comprehensive investigation of the scope of alcohol and carbonyl substrates, including scale-up to the gram level, our work also includes a detailed mechanistic analysis based on cyclic voltammetry, control experiments, and quantum chemical calculations. The study illustrates how electrolyte engineering can be effectively used for steering the selectivity in electro-organic synthesis.
ER -