Cyclization cascade of allenyl azides:: A dual mechanism
Cyclization cascade of allenyl azides:: A dual mechanism
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DOI：
10.1021/ja070818l
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发表时间：
2007-06-20
影响因子：
15
通讯作者：
Hester, D. Keith, II
中科院分区：
文献类型：
--
作者：
Silva Lopez, Carlos;Nieto Faza, Olalla;Hester, D. Keith, II
基于密度泛函理论，建立了一种描述联烯叠氮环加成级联反应机理的计算方法。这些计算的结果允许表征的关键活性中间体（双自由基和/或indolidopheres）和解释的共轭和非共轭物种之间的实验研究中观察到的不同行为。此外，某些中间体的计算分析提供洞察的区域选择性和立体选择性的情况下，不同的反应通道是在竞争中，建议适当的取代，以实现一个单一的区域异构体在吲哚合成通过叠氮丙二烯环化的问题。
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.