Nickel-catalyzed C-S coupling of challenging substrates

芳基硫醚是一类重要的化合物，直接用于农用化学品或医药工业等领域，或作为重要的合成中间体。金属催化的芳基氯化物和三氟化硫与硫醇的偶联反应是一种直接合成它们的方法。虽然已经有许多这种反应的例子，但它们通常有许多缺点(例如高温和催化剂负载)。此外，许多底物很难转化，因为它们的反应性(芳基氯化物)或由于空间位阻的原因。通过这个项目，我们希望缩小这一差距，并使用镍作为贱金属催化剂。我们的初步工作为我们的努力提供了良好的基础。其目的是确定催化剂和条件，以允许要求苛刻的底物耦合。同时，还计划开发新型对映选择性C-S偶联剂。力学研究是该项目的重要组成部分。除了解释催化循环的各个步骤外，它们还应为进一步改进催化剂提供必要的信息。

Aryl thioethers are important compounds that are directly used in many areas, such as agrochemical or pharmaceutical industry, or they serve as important synthetic intermediates. The metal-catalyzed coupling of aryl chlorides and triflates with thiols constitutes a direct method for their synthesis. Although there are already many examples of this reaction, they often have many disadvantages (e.g. high temperatures and catalyst loadings). In addition, many substrates are difficult to convert because of their reactivity (aryl chlorides) or for steric reasons. With this project, we want to close this gap and use nickel as a base metal catalyst. Our preliminary work provides a good basis for our effort. The aim is to identify catalysts and conditions that would allow the coupling of demanding substrates. At the same time, the development of novel enantioselective C-S couplings is planned. Mechanistic studies are an important part of the project. In addition to explaining the individual steps of the catalytic cycle, they should provide essential information for further improvement of the catalysts.