Cyclization Cascade of Allenyl Azides: Synergy Between Theory and Experiment.
Cyclization Cascade of Allenyl Azides: Synergy Between Theory and Experiment.
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DOI：
10.2174/138527210793563305
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发表时间：
2010-09-01
影响因子：
2.6
通讯作者：
López CS
中科院分区：
文献类型：
--
作者：
Faza ON;Feldman KS;López CS
实验学家和计算化学家之间的合作工作已经证明了一种强大的协同作用，这使得丙二烯基叠氮化物化学的合理化，并允许开发一种有效的合成工具，旨在制备几种生物碱。饱和的联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，而不饱和的联烯基叠氮化物形成吲哚烯中间体，其经由发生在Curtin-Hammett制度之外的电环闭环事件提供最终吲哚产物。与后者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）来操纵。
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.