Electrochemistry of Hypervalent Halogen Compounds

高价碘化合物由于其通用性和高效性，在有机合成中是一类重要的试剂。然而，从反应混合物中分离通常是有问题的，而且由于高昂的成本和安全问题，技术规模的应用尚未建立。项目(去掉符号)考虑到了这些问题，该项目旨在为原位生成碘(III)物种开发高效和节约资源的方法。研究了这类化合物的新代表的电化学生成，并测试了它们在有机转化中的介体作用。通过将芳基碘单元连接到离子基团，便于从产物混合物中分离，从而确保了可回收利用。同时，取消了配套电解液添加剂的使用，大大简化了产品混合物的分离。除了介体结构与电化学性质之间的关系外，高价卤素化合物在氧化偶联、环化反应和重排等方面的新应用也被开发出来。根据项目(去掉符号)工作中的发现，计划进一步探索高价卤素化合物的电化学。首先，开发的概念将转移到高价溴化合物上。尽管它们具有有趣的性质，但到目前为止，人们对后者的描述很少，这可以归因于它们的高反应性和从难以处理的三氟化溴开始的有问题的合成。因此，我们计划将芳基溴化物电化学转化为相应的溴化物，并随后测试它们作为不同转化媒介的适宜性。该项目的另一个重要方面是开发一种仅在亚化学计量比中使用芳基卤化物的电催化电池内过程。这在以前是不可能的，因为介体的氧化电位很高，这就是为什么必须使用化学计量比的ex-cell方法。为了实现电催化过程，项目描述中提出了几种介体结构和合适的应用。有机碘(V)化合物的电化学合成是计划中的项目的另一个目标。尽管它们作为氧化剂有着广泛的应用，但这类化合物的代表化合物的电化学合成还没有被描述。在这里，由于处理碘(V)试剂所涉及的风险，电化学原位生成的优势也是显而易见的。为了实现这一目标，人们提出了几种具有邻位稳定取代基的碘代芳烃结构。

Due to their versatility and efficiency, hypervalent iodine compounds represent an important class of reagents in organic synthesis. However, separation from the reaction mixture is usually problematic and application on the technical scale has not yet been established due to high costs and safety issues. These points were taken into account by project (sign removed), which aimed at developing efficient and resource-saving methods for the in-situ generation of iodine(III) species. The electrochemical generation of new representatives of this compound class was investigated and their use as mediators in organic transformations was tested. By tethering the aryl iodide unit to ionic groups, the separation from the product mixture was facilitated and thus recyclability was ensured. Simultaneously, the use of supporting electrolyte additives was rendered obsolete, which greatly simplified the separation of the product mixture. In addition to the correlation between mediator structure and electrochemical properties, new applications were developed in the fields of oxidative coupling, cyclization reactions and rearrangements.Based on the findings obtained during the work on project (sign removed), a further exploration of the electrochemistry of hypervalent halogen compounds is planned. First of all, the developed concept will be transferred to hypervalent bromine compounds. Despite their interesting properties, the latter have so far been little described, which can be ascribed to their high reactivity and the problematic synthesis starting from the difficult-to-handle bromine trifluoride. Therefore, we plan the electrochemical conversion of aryl bromides to the corresponding bromanes and to subsequently test their suitability as mediators for different transformations.A further important aspect of the project is the development of an electrocatalytic in-cell process in which the aryl halide is only used in sub-stoichiometric quantities. This was previously not possible due to the high oxidation potential of the mediators, which is why the stoichiometric ex-cell method had to be used. For the realization of electrocatalytic processes, several mediator structures and suitable applications are proposed in the project description.The electrochemical synthesis of organic iodine (V) compounds is another goal of the planned project. Despite their versatile application as oxidizing agents, electrochemical syntheses of representatives of this compound class have not yet been described. Here, too, the advantage of electrochemical in-situ generation is obvious due to the risks involved in handling iodine(V) reagents. To achieve this goal, several iodoarene structures with ortho-stabilizing substituents are proposed.