联烯基叠氮化物的环化级联反应：一种双重机制。
Cyclization cascade of allenyl azides: a dual mechanism.
作者信息
López Carlos Silva, Faza Olalla Nieto, Feldman Ken S, Iyer Malliga R, Ii D Keith Hester
机构信息
Departamento de Quimica Organica, Universidade de Vigo, Lagoas Marcosende, 36200 Vigo, Galicia, Spain.
出版信息
J Am Chem Soc. 2007 Jun 20;129(24):7638-46. doi: 10.1021/ja070818l. Epub 2007 May 27.
Abstract
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.
摘要
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。
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本文引用的文献
1
Nucleus-Independent Chemical Shifts: A Simple and Efficient Aromaticity Probe.核独立化学位移：一种简单高效的芳香性探针。
J Am Chem Soc. 1996 Jul 3;118(26):6317-6318. doi: 10.1021/ja960582d.
2
Allenyl azide cycloaddition chemistry. Synthesis of annelated indoles from 2-(allenyl)phenyl azide substrates.烯丙基叠氮环加成化学。从2-(烯丙基)苯基叠氮底物合成稠合吲哚。
Org Lett. 2006 Jul 6;8(14):3113-6. doi: 10.1021/ol061216u.
3
Allenyl azide cycloaddition chemistry. synthesis of pyrrolidine-containing bicycles and tricycles via the possible intermediacy of azatrimethylenemethane species.烯丙基叠氮环加成化学。通过氮杂三亚甲基甲烷物种可能的中间体合成含吡咯烷的双环和三环化合物。
J Am Chem Soc. 2005 Apr 6;127(13):4590-1. doi: 10.1021/ja050757w.
4
Theoretical study of the vinyl allene oxide to cyclopent-2-en-1-one rearrangement: mechanism, torquoselectivity and solvent effects.乙烯基环氧丙二烯重排为环戊-2-烯-1-酮的理论研究：机理、扭转选择性和溶剂效应
J Org Chem. 2004 May 28;69(11):3635-44. doi: 10.1021/jo049620z.
5
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density.将科勒-萨尔维蒂相关能公式发展为电子密度的泛函。
Phys Rev B Condens Matter. 1988 Jan 15;37(2):785-789. doi: 10.1103/physrevb.37.785.
6
Density-functional exchange-energy approximation with correct asymptotic behavior.具有正确渐近行为的密度泛函交换能近似
Phys Rev A Gen Phys. 1988 Sep 15;38(6):3098-3100. doi: 10.1103/physreva.38.3098.
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