Faza Olalla Nieto, Feldman Ken S, López Carlos Silva
Departamento de Quimica Organica, Universidade de Vigo, Lagoas Marcosende, 36200, Vigo, Galicia, Spain.
Curr Org Chem. 2010 Sep 1;14(15):1646-1657. doi: 10.2174/138527210793563305.
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.
实验化学家与计算化学家之间的合作已证明了一种强大的协同效应，这种效应使得烯丙基叠氮化学得以合理化，并促成了一种高效合成工具的开发，该工具旨在制备多种生物碱。饱和烯丙基叠氮会发生涉及关键双自由基中间体的反应级联，这些中间体遵循柯廷-哈米特模型，而不饱和烯丙基叠氮则形成吲哚烯中间体，这些中间体通过在柯廷-哈米特机制之外发生的电环化闭环反应生成最终的吲哚产物。通过向反应混合物中添加Cu(I)，可以控制后一种底物反应级联的区域化学。
