An investigation of the kinetics and mechanism of Cu(II)-catalyzed and ligandless CuAAC reactions

Cu(II) 催化和无配体 CuAAC 反应的动力学和机理研究

• 批准号: 2745682
• 金额: --
• 依托单位: University of St Andrews
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2022
• 资助国家: 英国
• 起止时间: 2022 至 无数据
• 项目状态: 未结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2745682
• 关键词: investigation; kinetics; mechanism; Cu; II

Recent work in the Watson group has challenged the prevailing literature surrounding copper-catalysed, azide alkyne cycloaddition (CuAAC) reactions. This project will aim to tackle three key aims stemming from these findings.1) The role of NaAsc. Prior work by Fokin posited that the Cu(I) catalysed system was 'ligandless', with supporting studies involving CuSO4 and NaAsc. Our group has found evidence, however, that NaAsc enhances the reaction and that it may be a ligand for Cu(I). This project will seek to establish if NaAsC is acting as a ligand and to probe and profile its effect on reaction kinetics.2) Cu(II) based CuAAC. These observations surrounding the effect of NaAsc were made alongside a discovery of a Cu(II)-promoted CuAAC reaction (using 2-ethynyl pyridine). To better understand if there is a greater generality to this mechanistic mode, this project with look at a (similarly) highly conjugated alkyne used by M.G. Finn, as shown below: This project will seek to profile the CuAAC reaction using the Finn alkyne and Cu(II), and, if Cu(II) catalysis seems operational, this reaction will be fully explored and charted.(3) Investigation of alkynyl phosphonates as Cu(II)-based CuAAC reagents. This will aim to build upon any findings within aim 2), with the idea of establishing a general (predictive) design criteria for the development of Cu(II)-based CuAAC reactions.

沃森集团（Watson Group）的最新工作挑战了围绕铜催化，叠氮化物环加成（CUAAC）反应的流行文献。该项目将旨在解决这些发现的三个关键目标。1）NAASC的作用。 Fokin的先前工作认为，Cu（I）催化系统是“配体”，其中涉及CUSO4和NAASC的支持研究。但是，我们的小组发现NAASC增强了反应，并且可能是Cu（i）的配体。该项目将寻求确定NAASC是否充当配体，并探测并介绍其对反应动力学的影响。2）基于Cu（II）的CuAAC。这些围绕NAASC效果的观察结果与发现Cu（II）促进的CuAAC反应（使用2-乙基吡啶）一起进行了。为了更好地理解这种机械模式是否具有更大的通用性，该项目具有M.G.使用的（类似）高度共轭炔烃的（类似）。 Finn，如下所示：该项目将寻求使用Finn Alkyne和Cu（II）来介绍CuAAC反应，如果Cu（ii）催化似乎有效，则将对此反应进行全面探索和绘制。（3）研究藻类磷酸盐作为Cu（II）基于CUAAC的CuAAc Reegents。这将旨在基于目标2）中的任何发现，并建立了基于Cu（II）基于CuAAC反应的一般（预测）设计标准的想法。