Anodic chlorine-mediated electrocatalytic conversion of aldehydes and nitrate to nitriles in a biphasic system

Nevertheless, further conversion of aldoximes into high-value nitriles still poses a critical challenge, due to the complex multistep reaction pathways and intrinsically unstable reaction intermediates. Herein, we report a novel anodic chlorine-mediated electroreduction strategy for the one-pot conversion of NO3- and aldehydes to nitriles using ZnPc/CNTs as the catalyst.

Cathodic semi-reduction of NO3- generates hydroxylamine (NH2OH), which undergoes condensation with aldehydes to form aldoximes, while anodically produced active chlorine species enable the chlorination of aldoximes to α-chlorooximes. Subsequent OH⁻-driven dehydrochlorination and electrocatalytic hydrodeoxygenation yield the target nitriles. The successful implementation of the overall reaction hinges on the cyclohexane gas buffer layer on top of the electrolyte that precisely regulates ClO⁻ concentration to match the kinetics of the cascade reaction, thereby achieving 99% selectivity and a maximum formation rate of 18.7 μmol·cm-2·h-1 for benzonitrile.