Modicom Florian, Jamieson Ellen M G, Rochette Elise, Goldup Stephen M
Chemistry, University of Southampton, Highfield, Southampton, SO17 1BJ, UK.
Angew Chem Int Ed Engl. 2019 Mar 18;58(12):3875-3879. doi: 10.1002/anie.201813950. Epub 2019 Feb 14.
We report the unexpected discovery of a tandem active template CuAAC-rearrangement process, in which N is extruded on the way to the 1,2,3-triazole product to give instead acrylamide rotaxanes. Mechanistic investigations suggest this process is dictated by the mechanical bond, which stabilizes the Cu -triazolide intermediate of the CuAAC reaction and diverts it down the rearrangement pathway; when no mechanical bond is formed, the CuAAC product is isolated.
我们报道了串联活性模板铜催化的叠氮-炔环加成重排反应这一意外发现，在此过程中，在生成1,2,3-三唑产物的途中氮被挤出，取而代之得到丙烯酰胺轮烷。机理研究表明，该过程由机械键决定，机械键使铜催化的叠氮-炔环加成反应的铜-三唑化物中间体稳定，并使其转向重排途径；当未形成机械键时，则分离得到铜催化的叠氮-炔环加成反应产物。
Zotero 插件
