Studies towards Enantioselective Silver-Catalysed C-H Amination via Nitrene Transfer using Multi-Functional Ligands

第一年：为CDT所有一年级学生成员提供一般培训活动。第2-4年：通过硝基转移（NT）的C-H胺化能够将C-H键直接转化为C-N键，并具有改变含氮分子合成的潜力。在过去的25年里，NT反应作为交叉偶联反应的一种替代方法得到了广泛的关注。虽然C-H胺化反应的化学选择性和位点选择性现在已经很好地建立起来，但对映体选择性仍然是一个挑战。通常情况下，需要复杂的手性配体才能看到给定底物类的任何对映体诱导。最近，银因其广泛的配位几何形状和在反应物和配体之间进行非共价相互作用（nci）的能力而引起了人们的兴趣。通过NT对映选择性银催化的C-H胺化很少被探索，迄今为止只有少数例子成功开发。我们的小组已经成功地表明，C-H硼化反应中的对映体选择性可以通过与铱的非手性阴离子配体相关的手性阳离子来控制。由于该方法具有广泛应用于其他过渡金属（TM）催化反应的潜力，离子配对配体系统将采用银催化的C-H胺化方案进行研究。

Year 1: Generic training activities for all first-year student members of the CDT.Year 2-4: C-H amination via nitrene transfer (NT) is able to convert C-H bonds directly to C-N bonds and holds the potential to transform the synthesis of nitrogen-containing molecules. NT reactions have gained much interest in the last 25 years as an alternative to cross-coupling reactions. Whilst chemo- and site-selectivity in C-H amination reactions is now well established, enantioselectivity is still a challenge. It is often the case that elaborate chiral ligands are required to see any enantioinduction for a given substrate class. Recently, silver has gained interest for its wide range of coordination geometries and ability to host non-covalent interactions (NCIs) between reactants and ligands. Enantioselective silver-catalysed C-H amination via NT has been seldom explored with only a handful of examples successfully developed thus far. Our group has successfully shown that enantioselectivity in C-H borylation can be controlled by a chiral-cation that is associated with an achiral, anionic ligand for iridium. With the potential for this methodology to be broadly applied to a range of other transition metal (TM) catalysed reactions, the ion-paired ligand system will be investigated with a silver-catalysed C-H amination protocol.