Synthesis of Polycyclic Aminocyclobutane Systems by the Rearrangement of N‐(ortho‐Vinylphenyl) 2‐Azabicyclo[3.1.0]hexane Derivatives |
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| Authors: | Agnieszka Wasilewska Bartosz A. Woźniak Dr. Gabriel Doridot Kamila Piotrowska Natalia Witkowska Dr. Pascal Retailleau Dr. Yvan Six |
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| Affiliation: | 1. Laboratoire de Synthèse Organique DCSO, UMR 7652 CNRS/Ecole Polytechnique, 91128 Palaiseau Cedex (France), Fax: (+33)?1‐6933‐5972;2. Faculty of Chemistry, Nicolaus Copernicus University, Gagarina 7, 87‐100 Toruń (Poland);3. Centre de recherche de Gif, Institut de Chimie des Substances Naturelles, CNRS, avenue de la Terrasse, 91198 Gif‐sur‐Yvette Cedex (France);4. Department of Chemistry, Faculty of Organic Stereochemistry, Adam Mickiewicz University, Umultowska 89B, 61‐614 Poznań (Poland) |
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| Abstract: | 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. |
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| Keywords: | electrocyclic reactions iminium compounds microwave chemistry small ring systems titanium |
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