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首页> 外文期刊>Chemistry: A European journal >Highly strained 2,3-bridged 2H-azirines at the borderline of closed-shell molecules
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Highly strained 2,3-bridged 2H-azirines at the borderline of closed-shell molecules

机译：高应变的2,3-桥联2H-叠氮基在封闭壳分子的边界处

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摘要

Substituted 1-azidocyclopentenes and 1-azidocyclohexenes were photolyzed to generate 2,3-bridged 2H-azirines. In the case of bridgehead azirines with a six-membered carbocycle, detection by NMR spectroscopic analysis was possible, whereas even kinetically stabilized bridgehead azirines with a five-membered ring could not be characterized by lowerature NMR spectroscopic analysis. Thus, a recent report on the latter heterocycles was corrected. Depending on the substitution pattern, irradiation of 1-azidocyclopentenes either led to products that can be explained on the basis of short-lived 2,3-bridged 2H-azirines, or gave secondary products generated from triplet nitrenes. The diverse photoreactivity of 2,3-bridged 2H-azirines was also studied by quantum chemical methods (DFT, CCSD(T), CASSCF(6,6)) with respect to the singlet and triplet energy surfaces. The ring-opening processes leading to the corresponding vinyl nitrenes were identified as key steps for the observed reactivity.
机译：取代的1-叠氮环戊烯和1-叠氮环己烯被光解生成2,3-桥联的2H-叠氮基。在具有六元碳环的桥头叠氮基的情况下，可以通过NMR光谱分析进行检测，而即使具有五元环的动力学稳定的桥头叠氮基也无法通过低级NMR光谱分析来表征。因此，最新的关于后者杂环的报告已得到纠正。根据取代方式的不同，对1-叠氮环戊烯的辐照要么生成可以基于短寿命的2，3-桥连的2H-叠氮基来解释的产物，要么生成由三重态亚硝基生成的次级产物。还通过量子化学方法（DFT，CCSD（T），CASSCF（6,6））研究了相对于单重态和三重态能量表面的2,3-桥联2H-叠氮基的各种光反应性。导致相应的乙烯基腈的开环过程被确定为观察到的反应性的关键步骤。

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