Giel Marie-Claire, Smedley Christopher J, Mackie Emily R R, Guo Taijie, Dong Jiajia, Soares da Costa Tatiana P, Moses John E
La Trobe Institute for Molecular Science, La Trobe University, Melbourne, VIC, 3086, Australia.
Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai, 200032, P. R. China.
Angew Chem Int Ed Engl. 2020 Jan 13;59(3):1181-1186. doi: 10.1002/anie.201912728. Epub 2019 Nov 28.
The boom in growth of 1,4-disubstituted triazole products, in particular, since the early 2000's, can be largely attributed to the birth of click chemistry and the discovery of the Cu -catalyzed azide-alkyne cycloaddition (CuAAC). Yet the synthesis of relatively simple, albeit important, 1-substituted-1,2,3-triazoles has been surprisingly more challenging. Reported here is a straightforward and scalable click-inspired protocol for the synthesis of 1-substituted-1,2,3-triazoles from organic azides and the bench stable acetylene surrogate ethenesulfonyl fluoride (ESF). The new transformation tolerates a wide selection of substrates and proceeds smoothly under metal-free conditions to give the products in excellent yield. Under controlled acidic conditions, the 1-substituted-1,2,3-triazole products undergo a Michael addition reaction with a second equivalent of ESF to give the unprecedented 1-substituted triazolium sulfonyl fluoride salts.
特别是自21世纪初以来，1,4-二取代三唑产物的增长热潮在很大程度上可归因于点击化学的诞生以及铜催化的叠氮化物-炔烃环加成反应（CuAAC）的发现。然而，相对简单（尽管很重要）的1-取代-1,2,3-三唑的合成却出人意料地更具挑战性。本文报道了一种直接且可扩展的受点击反应启发的方法，用于从有机叠氮化物和实验室稳定的乙炔替代物乙烯磺酰氟（ESF）合成1-取代-1,2,3-三唑。这种新的转化方法能耐受多种底物，并在无金属条件下顺利进行，以优异的产率得到产物。在受控的酸性条件下，1-取代-1,2,3-三唑产物与第二当量的ESF发生迈克尔加成反应，得到前所未有的1-取代三唑鎓磺酰氟盐。
