4.7 Article

Mechanistic investigation of electrocatalytic reductive amination at copper electrode

Journal

CHEMICAL COMMUNICATIONS
Volume 59, Issue 32, Pages 4818-4821

Publisher

ROYAL SOC CHEMISTRY
DOI: 10.1039/d3cc00296a

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This study reports an electrochemical reductive amination method for sustainable synthesis. Cu metal electrodes achieved Faradaic efficiencies of about 83%. The origin of protons during the electrochemical reductive amination process was scrutinized through experiments with deuterated solvent and additional proton sources. CW-EPR analysis captured the radical intermediate species formed during the catalytic cycle, advancing the mechanistic understanding of electrochemical reductive amination.
Reductive amination has been widely used for manufacturing carbon-nitrogen-containing building blocks. Despite its versatility, the need for a chemical reductant or harmful hydrogen gas has limited its further utilization in modern chemical applications. Here, we report electrochemical reductive amination (ERA) to pursue sustainable synthetic routes. Faradaic efficiencies of about 83% are achieved using Cu metal electrodes. In-depth electrokinetic studies reveal the rate-determining step and overall reaction nature of ERA. Through the experiments using deuterated solvent and additional proton sources, we scrutinize the origin of protons during the ERA. Furthermore, CW-EPR analysis captures the radical intermediate species, formed during the catalytic cycle, advancing mechanistic understanding of ERA process.

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