Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich-Schiller-University Jena, Humboldtstr. 10, 07743 Jena, Germany.
Chem Asian J. 2011 Oct 4;6(10):2816-24. doi: 10.1002/asia.201100404. Epub 2011 Aug 31.
[3+2]-cycloaddition reactions of aromatic azides and silylated alkynes in aqueous media yield 1,5-disubstituted-4-(trimethyl-silyl)-1H-1,2,3-triazoles. The formation of the 1,5-isomer is highly favored in this metal-free cycloaddition, which could be proven by 1D selective NOESY and X-ray investigations. Additionally, DFT calculations corroborate the outstanding favoritism regarding the 1,5-isomer. The described method provides a simple alternative protocol to metal-catalyzed "click chemistry" procedures, widening the scope for regioselective heavy-metal-free synthetic applications.
在水相介质中，芳香叠氮化物和硅基炔烃的[3+2]-环加成反应生成 1,5-二取代-4-(三甲基硅基)-1H-1,2,3-三唑。在这种无金属的环加成反应中，1,5-异构体的形成非常有利，这可以通过 1D 选择性 NOESY 和 X 射线研究来证明。此外，DFT 计算也证实了 1,5-异构体的显著优势。所描述的方法为金属催化的“点击化学”程序提供了一种简单的替代方案，拓宽了区域选择性无重金属合成应用的范围。
