Anodically Generated Platform Oxidizers as an Alternative to Oxygen Evolution and Anodically (Re)generated Electrocatalysts for Selective Conversion of Organic Compounds

该次级项目的中心目标是直接延续第一个资助期。其中，主要的焦点是使用掺硼的金刚石阳极有效地生成大部分未被开发的过氧二碳酸酯(PODIC)，以及在有机合成中的应用。在第二个资助期，重点将放在合成更易储存和“稳定”的高性能氧化剂过硼酸盐(或过氧硼酸盐)和高碘酸盐上，因为PODIC的使用寿命有限。此外，还将研究PODIC的其他应用。例子包括芳基硼酸的异羟基化和木质素衍生的4-羟基苯甲醛氧化成相应的对苯二酚/对苯二酚等。过硼酸盐的电合成将在专门设计的流动电解槽中进行，使用我们从第一个资助期获得的知识。此外，我们还将开发一种大型电解槽，以增加每小时形成的过氧碳酸氢盐的量，使反应能够从十克到公斤级。这些工作包将与卢卡斯古昂(TP6)密切合作，建立在我们从第一个资助期开始的卓有成效的合作基础上。工作包的另一个子集将涉及木质素、酒精和胺氧化降解的电催化以及一种新的卤仿类型反应的研究。这将与舒曼(TP1)和贝伦(TP8)小组合作完成。此外，还将从与Aliaksandr Bandarenka(TP5)和Martin Muhler(TP7)的合作中获得机械论的见解。

The central goal of the subproject is a direct continuation of the first funding period. Therein, the main focus was the efficient generation of the largely underexplored peroxodicarbonate (PODIC) using boron-doped diamond anodes and the use of PODIC in organic syntheses. In the second funding period the focus will be laid on the synthesis of the more storable and “bench-stable” high performance oxidizers perborate (or peroxoborate) and periodate, as PODIC possesses only a limited life-time. Furthermore, other applications of PODIC will be investigated. Examples include the ipso-hydroxylation of aryl boronic acids and the oxidation of lignin-derived 4-hydroxy benzaldehydes to the respective quinones/hydroquinones, among others. The electrosynthesis of perborate will be conducted in specifically designed flow-electrolyzers, using our gained knowledge from the first funding period. Additionally, we will develop a large-scale electrolyzer to increase the amount of peroxodicarbonate formed per hour, enabling decagram to kilogram scale reactions. These work packages will be conducted in close cooperation with Lukas Gooßen (TP6), building upon our fruitful collaboration from the first funding period. Another subset of work packages will deal with the investigation of electro-catalysis for the degradation of lignin, alcohol, and amine oxidation as well as a novel haloform-type reaction. This will be done in cooperation with both the Schuhmann (TP1) and Behrens (TP8) groups. Furthermore, mechanistic insights will be gained from collaborations with both Aliaksandr Bandarenka (TP5) and Martin Muhler (TP7).