Laboratoire de Synthèse Organique DCSO, UMR 7652 CNRS/Ecole Polytechnique, 91128 Palaiseau Cedex, France.
Chemistry. 2013 Aug 26;19(35):11759-67. doi: 10.1002/chem.201300871. Epub 2013 Jul 12.
The acid-catalysed thermal rearrangements of a family of N-aryl 2-azabicyclo[3.1.0]hexanes is described. These substrates, designed in such a way that the aromatic system is conjugated with an alkene group located at the ortho position relative to the nitrogen atom, have been prepared by using an intramolecular Kulinkovich-de Meijere reaction. The rearrangements can then be conducted either under standard thermal conditions or with microwave activation. Depending on the conditions applied and the substitution pattern, dihydroquinoline or polycyclic aminocyclobutane derivatives can be obtained. A mechanistic discussion is provided, with the proposition of the initial protonation of the aminocyclopropane moiety to give an iminium intermediate. By analogy with related intermolecular reactions, the involvement of electrocyclic reactions among the series of elementary steps that follow is put forward.
描述了一系列 N-芳基 2-氮杂双环[3.1.0]己烷的酸催化热重排反应。这些底物的设计方式是使芳环系统与位于氮原子邻位的烯烃基团共轭，通过使用分子内 Kulinkovich-de Meijere 反应来制备。重排可以在标准热条件下或微波激活下进行。根据所应用的条件和取代模式，可以得到二氢喹啉或多环氨基环丁烷衍生物。提供了一个机理讨论，提出了氨基环丙烷部分的初始质子化以得到亚胺中间体。通过与相关的分子间反应类比，提出了后续一系列基元反应中环加成反应的参与。
