Iacobucci Claudio, Lebon Alexandre, De Angelis Francesco, Memboeuf Antony
UMR CNRS 6521, CEMCA, Université de Bretagne Occidentale, 6 Av. Le Gorgeu, CS 93837, 29238, Cedex 3, France.
Department Physical and Chemical Sciences, University of L'Aquila, Via Vetoio, 67100, L'Aquila, Italy.
Chemistry. 2016 Dec 23;22(52):18690-18694. doi: 10.1002/chem.201603518. Epub 2016 Nov 23.
Copper-catalysed azide alkyne cycloaddition (CuAAC) has been considered a breakthrough transformation over the last 15 years. Its debated mechanism arouses continuously growing interest. By means of a mass spectrometer modified ad hoc, the entire catalytic cycle of CuAAC reaction has been investigated in the gas phase. Ion-molecule reactions were performed inside the mass spectrometer to reproduce step-by-step, at a molecular level, the complete catalytic cycle of the click reaction. We successfully challenged the reactivity of elusive mono- and bis-copper intermediates by ion-molecule reactions leading to the production of mass-characterized triazole products, paving the way for detailed energetic studies to be performed in the gas phase. The structures of the relevant species, calculated at a DFT level, helped rationalise our experimental results.
在过去15年里，铜催化的叠氮化物-炔烃环加成反应（CuAAC）被视为一项突破性的转化反应。其备受争议的反应机理引发了人们持续增长的兴趣。借助专门改装的质谱仪，在气相中对CuAAC反应的整个催化循环进行了研究。在质谱仪内部进行离子-分子反应，以便在分子层面上逐步重现点击反应的完整催化循环。我们通过离子-分子反应成功挑战了难以捉摸的单铜和双铜中间体的反应活性，从而生成了具有质量特征的三唑产物，为在气相中进行详细的能量研究铺平了道路。在密度泛函理论（DFT）水平上计算得到的相关物种的结构，有助于我们对实验结果作出合理的解释。
