On the Use of Polyelectrolytes and Polymediators in Organic Electrosynthesis

Although organic electrosynthesis is generally considered to be a green method, the necessity for excess amounts of supporting electrolyte constitutes a severe drawback. Furthermore, the employment of redox mediators results in an additional separation problem. In this context, we have explored the applicability of soluble polyelectrolytes and polymediators with the TEMPO‐mediated transformation of alcohols into carbonyl compounds as a test reaction. Catalyst benchmarking based on cyclic voltammetry studies indicated that the redox‐active polymer can compete with molecularly defined TEMPO species. Alcohol oxidation was also highly efficient on a preparative scale, and our polymer‐based approach allowed for the separation of both mediator and supporting electrolyte in a single membrane filtration step. Moreover, we have shown that both components can be reused multiple times.