Shastin Alexey V, Tsyrenova Biligma D, Sergeev Pavel G, Roznyatovsky Vitaly A, Smolyar Ivan V, Khrustalev Victor N, Nenajdenko Valentine G
Department of Chemistry , Lomonosov Moscow State University , 119899 Moscow , Russia.
Institute of Problems of Chemical Physics , Russian Academy of Sciences , 142432 Chernogolovka , Russia.
Org Lett. 2018 Dec 21;20(24):7803-7806. doi: 10.1021/acs.orglett.8b03227. Epub 2018 Nov 30.
The reaction of 4,4-dichloro-1,2-diazabuta-1,3-dienes with sodium azide has been studied and found to provide straightforward access to extremely rare 1,1-bisazides. It was demonstrated that these highly unstable compounds are prone to eliminate the N molecule to cyclize into 4-azido-1,2,3-triazoles bearing two aryl (heteroaryl) groups at positions 2 and 5. The formation of bisazides was confirmed by their trapping with cyclooctyne and B3LYP calculations. Most likely, the elimination of nitrogen to form an intermediate nitrene is facilitated by the aza group via anchimeric-like participation. The reaction was found to be very general for the highly efficient synthesis of various 4-azidotriazoles. It was demonstrated that these heterocycles are highly attractive building blocks for subsequent preparation of 1,2,3-triazole-derived compounds.
对4,4-二氯-1,2-二氮杂丁二烯-1,3-二烯与叠氮化钠的反应进行了研究，发现该反应能直接得到极为罕见的1,1-双叠氮化合物。结果表明，这些高度不稳定的化合物易于消除N分子，环化生成在2位和5位带有两个芳基（杂芳基）的4-叠氮基-1,2,3-三唑。通过环辛炔捕获双叠氮化合物并进行B3LYP计算，证实了双叠氮化合物的形成。最有可能的是，氮杂基团通过类似邻基参与的方式促进了氮的消除以形成中间体氮烯。该反应对于高效合成各种4-叠氮基三唑非常通用。结果表明，这些杂环是后续制备1,2,3-三唑衍生化合物极具吸引力的结构单元。
