Integrated Electro‐Biocatalysis for Amine Alkylation with Alcohols

The integration of electro and bio‐catalysis offers new ways of making molecules under very mild, environmentally benign conditions. We show that TEMPO mediated electro‐catalytic oxidation of alcohols can be adapted to work in aqueous buffers, with minimal organic co‐solvent, enabling integration with biocatalytic reductive amination using the Ad RedAm enzyme. The combined process offers a new approach to amine alkylation with native alcohols, a key bond formation in the chemical economy that is currently achieved via precious metal‐catalyzed hydrogen‐borrowing technologies. The electrobio transformation is effective for primary and secondary alcohols undergoing coupling with allyl, propargyl, benzyl, and cyclopropyl amines, and has been adapted for use with solid‐supported Ad RedAM for ease of operation.