Collaborative work between experimentalists and computational chemists have demonstrated a stong synergy which allowed the rationalization of allenyl azide chemistry and permited the development of an efficient synthetic tool aimed at the preparation of several alkaloids. Saturated allenyl azides undergo a reaction cascade involving key diradical intermediates that follow the Curtin-Hammett model whereas unsaturated allenyl azides form indolidene intermediates that furnish the final indole products via electrocyclic ring closure events taking place out of the Curtin-Hammett regime. The regiochemistry of the reaction cascade with the latter substrates can be manipulated by Cu(I) addition to the reaction mixture.

中文翻译：

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烯基叠氮化物的环化级联：理论与实验的协同作用

实验家和计算化学家之间的合作工作已经证明了强大的协同作用，这使得联烯基叠氮化物化学合理化，并允许开发一种旨在制备几种生物碱的有效合成工具。饱和的烯基叠氮化物经历涉及遵循 Curtin-Hammett 模型的关键双自由基中间体的反应级联反应，而不饱和的烯基叠氮化物形成吲哚基中间体，通过在 Curtin-Hammett 体系之外发生的电环闭环事件提供最终的吲哚产物。与后一种底物的反应级联的区域化学可以通过向反应混合物中添加 Cu(I) 来控制。