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.

Watson小组最近的工作挑战了围绕铜催化的叠氮炔环加成反应(CuAAC)的主流文献。该项目将致力于解决由这些发现产生的三个关键目标。1)NaAsc的作用。Fokin之前的工作假设铜(I)催化体系是‘无配体’的，并支持涉及CuSO4和NaAsc的研究。然而，我们的团队已经发现证据表明，NaAsc增强了反应，并且它可能是铜(I)的配体。这个项目将寻求确定NaAsC是否作为配体，并探索和描述其对反应动力学的影响。2)基于铜(II)的CuAAC。这些围绕NaAsc影响的观察是在发现铜(II)促进的CuAAC反应(使用2-乙炔基吡啶)的同时进行的。为了更好地了解这种机理模式是否有更大的普遍性，本项目与M.G.Finn使用的(类似的)高共轭乙炔进行了研究，如下所示：该项目将寻求使用Finn乙炔和铜(II)来描述CuAAC反应，如果Cu(II)催化似乎是可行的，则将充分探索和绘制该反应的图表。(3)作为基于铜(II)的CuAAC试剂的炔基膦的研究。这将旨在建立在目标2)内的任何发现的基础上，想法是为基于铜(II)的CuAAC反应的发展建立一个通用(预测性)设计标准。