Emerging strategies for electrochemical C-N bond formation

The work in this PhD thesis describes new endeavors in the development and design of electrochemical C–N bond forming reactions. The goal of this work was to combine the fields of electrosynthesis and electrocatalysis, so that new electrocatalysts could be developed that are tailored to specific reactions. Amino acids, amines and amides were made with specific catalysts, as these molecules comprise most of the organic molecules that contain a C–N bond. To synthesize amino acids, a copper electrocatalyst was used that was modified with one monolayer of lead to inhibit the parasitic hydrogen evolution reaction. A nickel oxyhydroxide and silver catalyst were combined in a linear paired electrolysis reaction to transform alcohols into amines, a process that normally requires elevated temperatures and pressures or the use of stoichiometric redox reactions. A redox active polymer was synthesized containing TEMPO moieties that could convert methanol to formaldehyde with excellent selectivity. Finally, the methanol oxidation reaction was studied further to synthesize several formamides. Notable in this research was that the formamide synthesis went through an isocyanide intermediate, which was previously not observed. All in all, this thesis shows the capability of electrocatalysis to aid in the synthesis of important organic building block molecules in future research and industry.