Unfunctionalised Arenes in Cross-Coupling Processes

碳氢键是有机分子中最常见的键。在该提案中，我们描述了一项研究，以开发允许这些键用作形成有用的碳-碳键的方法。拟议的研究涉及开发乙烯基三氟甲磺酸酯（或卤化物）和简单的芳基之间的钯催化偶联反应C-H系统。使用芳基C-H体系作为偶联反应中的组分之一的能力提供了优于双偶联方法的显著优点;其中最重要的是易于合成所需的偶联配偶体和显著减少所产生的废副产物的量。该项目将侧重于分子内耦合，即，该项目的初始阶段将使用平行筛选方法确定有效的催化剂系统。这些模型系统也将被用来探测不同的电子和立体取代基的环化效率的影响。该项目的第二阶段是探索已开发化学的范围。首先将研究碳环体系，然后再评估杂环体系的合成。该项目的最后阶段将尝试将已开发的环化化学与钯催化反应相结合，以开发新的反应级联。这些多米诺骨牌序列将使用简单易得的起始材料在一锅反应中产生复杂的系统。

Carbon-hydrogen bonds are the most common bonds found in organic molecules. In this proposal we describe an investigation to develop methods that allows these bonds to be used as handles for the formation of useful carbon-carbon bonds.The proposed research is concerned with developing palladium catalysed coupling reactons between vinyl triflates (or halides) and simple aryl C-H systems. The ability to use aryl C-H systems as one of the components in a coupling reaction offers significant advantages over exisiting methods; paramount amongst these are the ease of synthesis of the required coupling partners and the significant reduction in the amount of waste byproducts generated. The project will focus on intramolecular couplings, i.e., cyclisation reactions.The initial phase of the project will define efficient catalyst systems using parallel screening methods. These model systems will also be used to probe the effects of different electronic and streric substituents on the efficiency of the cyclisations. The second phase of the project is to explore the scope of the developed chemistry. Initially carbocyclic systems will be studied before moving on to evaluate the synthesis of heterocyclic systems. The final phase of the project will attempt to combine the developed cyclisation chemistry with exisiting palladium catalysed reactions to develop new reaction cascades. These domino sequences will use simple readily available starting materials to produce complex systems in one-pot reactions.