Institute of Chemistry, Rostock University, Albert-Einstein-Str. 3a, 18059, Rostock, Germany.
Angew Chem Int Ed Engl. 2018 Jan 8;57(2):422-426. doi: 10.1002/anie.201710659. Epub 2017 Dec 12.
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.
尽管有机电化学合成通常被认为是一种绿色方法，但需要过量的支持电解质这一点构成了严重的缺点。此外，使用氧化还原介质会导致额外的分离问题。在这种情况下，我们探索了可溶性聚合物电解质和聚合物介质在 TEMPO 介导的醇转化为羰基化合物反应中的应用，以此作为测试反应。基于循环伏安法研究的催化剂基准测试表明，氧化还原活性聚合物可以与分子定义的 TEMPO 物质竞争。醇氧化在制备规模上也非常高效，我们的聚合物方法允许在单个膜过滤步骤中分离介质和支持电解质。此外，我们还表明，这两种成分都可以多次重复使用。
