The Key Laboratory of Molecular Engineering of Polymers, Ministry of Education, Department of Macromolecular Science, and Laboratory of Advanced Materials, Fudan University, Shanghai 200433, People's Republic of China.
J Phys Chem A. 2010 Aug 19;114(32):8331-6. doi: 10.1021/jp105034m.
A designed ligand-accelerated Cu(I)-catalyzed cycloaddition (CuAAC) reaction was monitored for the first time by real time infrared analysis technique based on ATR-FTIR principles. Principal components analysis (PCA) and two-dimensional correlation spectroscopy (2Dcos) results showed that the consumption of alkyne and azide took place successively followed by the formation of the product 1,2,3-triazole, and a 1:1 complex of two reactants would be formed in the reaction process. The rate-determining step of the CuAAC reaction was also experimentally confirmed for the first time to be the transition of azide-alkyne 1:1 complex to the preproduct 1,2,3-triazole. Our results are in good conformity with the current catalytic mechanism proposed by Sharpless et al. according to DFT calculation results.
首次通过基于 ATR-FTIR 原理的实时红外分析技术监测到设计配体加速的 Cu(I)-催化环加成 (CuAAC) 反应。主成分分析 (PCA) 和二维相关光谱 (2Dcos) 结果表明，炔烃和叠氮化物的消耗依次发生，随后形成 1,2,3-三唑产物，并且在反应过程中会形成两种反应物的 1:1 络合物。首次通过实验证实，CuAAC 反应的速率决定步骤是叠氮化物-炔烃 1:1 络合物向预产物 1,2,3-三唑的转变。根据 DFT 计算结果，我们的结果与 Sharpless 等人提出的当前催化机制非常吻合。
