Sulfonium salts as pseudohalide electrophiles for cross-coupling having improved tractability, orthogonality, stability and environmental profile

目的：合成在交叉偶联反应中用作伪卤化物的磺化盐。目标：1)优化磺化盐的形成2)合成不同化学性质的磺化盐3)在交叉偶联反应中使用磺化盐，如铃木交叉偶联，作为伪卤化物4)进行交叉偶联的机理研究本研究的潜在应用是在化学工业和学术界实现新的合成方法。在过去的几十年里，所谓的“交叉偶联”反应已经成为化学合成的一个名称，其重要性在2010年的诺贝尔奖中得到了认可。然而，现有交叉耦合方法仍然存在显著的局限性。所提出的磺胺盐可用于交叉偶联反应，其中相应的卤化物（“传统”起始材料）不稳定，单卤化物难以形成或难以纯化等，因此可以通过交叉偶联反应获得更广泛的分子。这项研究的好处是，硫鎓盐更容易处理，通常比它们所取代的卤化物更稳定，并且在交叉耦合中作为亲电试剂的伪卤化物具有更好的环境特征。该项目与EPSRC的“未来制造技术”和“先进材料”的交叉切割能力相一致，因此与研究委员会的目标相关。二级导师Catherine Lyall博士在核磁共振光谱方面具有专业知识，因此将协助使用动态反应监测流核磁共振设施进行计划的机制研究

Aim - Synthesise sulfonium salts for use as pseudo halides in cross-coupling reactions.Objectives - 1) Optimise formation of sulfonium salts 2) Synthesise sulfonium salts of varying chemical nature 3) Usesulphonium salts in cross coupling reactions such as Suzuki Cross Couplings, as pseudo halides 4)Performmechanistic studies for the cross-couplingThe potential applications of this research, are to enable new methods od synthesis in both the chemical industry andacademia, so called 'cross coupling' reactions have become a name stay of chemical synthesis over the last fewdecades and their significance was acknowledged in the 2010 Nobel Prize. However, significant limitations remain inthe existing cross coupling methodology. The proposed sulphonium salts can be used in cross coupling reactionswhere the corresponding halide (the 'traditional' starting material) is unstable, the monohalide is difficult to form orchallenging to purify etc. and so enables access to a wider range of molecules through cross coupling reactions.The benefits of this research are that sulphonium salts are easier to handle, are usually more stable than the halidesthey are replacing, and have a better environmental profile as pseudo halides for electrophiles in cross couplingsThe project aligns with the EPSRC cross cutting capabilities of 'future manufacturing technologies' and 'advancedmaterials' so is therefore relevant to the goals of the research council.The secondary supervisor, Dr. Catherine Lyall has expertise in NMR spectroscopy and therefore will assist withplanned mechanistic studies using the Dynamic Reaction Monitoring Flow NMR facility