Díaz Velázquez Heriberto, Ruiz García Yara, Vandichel Matthias, Madder Annemieke, Verpoort Francis
Laboratory of Organometallics, Catalysis and Ordered Materials, State Key Laboratory of Advanced Technology for Materials Synthesis and Processing; Center for Chemical and Material Engineering, Wuhan University of Technology; Department of Applied Chemistry, Faculty of Sciences, Wuhan University of Technology, Wuhan 430070, P.R. China.
Org Biomol Chem. 2014 Dec 14;12(46):9350-6. doi: 10.1039/c4ob01350f. Epub 2014 Sep 24.
Copper(I)-catalyzed 1,3-dipolar cycloaddition of azides and terminal alkynes (CuAAC), better known as "click" reaction, has triggered the use of 1,2,3-triazoles in bioconjugation, drug discovery, materials science and combinatorial chemistry. Here we report a new series of water-soluble catalysts based on N-heterocyclic carbene (NHC)-Cu complexes which are additionally functionalized with a sulfonate group. The complexes show superior activity towards CuAAC reactions and display a high versatility, enabling the production of triazoles with different substitution patterns. Additionally, successful application of these complexes in bioconjugation using unprotected peptides acting as DNA binding domains was achieved for the first time. Mechanistic insight into the reaction mechanism is obtained by means of state-of-the-art first principles calculations.
铜（I）催化的叠氮化物与末端炔烃的1,3-偶极环加成反应（CuAAC），更广为人知的是“点击”反应，引发了1,2,3-三唑在生物共轭、药物发现、材料科学和组合化学中的应用。在此，我们报道了一系列基于N-杂环卡宾（NHC）-铜配合物的新型水溶性催化剂，这些配合物还被磺酸基团功能化。这些配合物对CuAAC反应表现出卓越的活性，并具有高度的通用性，能够制备具有不同取代模式的三唑。此外，首次成功地将这些配合物应用于生物共轭，使用未受保护的肽作为DNA结合域。通过最先进的第一性原理计算获得了对反应机理的机理洞察。
