López Carlos Silva, Faza Olalla Nieto, Feldman Ken S, Iyer Malliga R, Ii D Keith Hester
Departamento de Quimica Organica, Universidade de Vigo, Lagoas Marcosende, 36200 Vigo, Galicia, Spain.
J Am Chem Soc. 2007 Jun 20;129(24):7638-46. doi: 10.1021/ja070818l. Epub 2007 May 27.
A density functional theory based computational approach to describing the mechanistic course of the allene azide cycloaddition cascade sequence has been developed. The results of these calculations permit characterization of key reactive intermediates (diradicals and/or indolidenes) and explain the different behaviors observed in the experimental studies between conjugated and nonconjugated species. Furthermore, computational analysis of certain intermediates offer insight into issues of regioselectivity and stereoselectivity in cases where different reaction channels are in competition, suggesting suitable substitutions to achieve a single regioisomer in the indole synthesis via azide-allene cyclization.
已开发出一种基于密度泛函理论的计算方法，用于描述丙二烯叠氮化物环加成级联序列的反应机理。这些计算结果能够对关键反应中间体（双自由基和/或吲哚烯）进行表征，并解释在共轭和非共轭物种的实验研究中观察到的不同行为。此外，对某些中间体的计算分析有助于深入了解不同反应通道相互竞争情况下的区域选择性和立体选择性问题，为通过叠氮化物-丙二烯环化在吲哚合成中实现单一区域异构体提出合适的取代基。
