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Metal‐Free Cyclization of ortho‐Nitroaryl Ynamides and Ynamines towards Spiropseudoindoxyls |
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| Authors: | Niels Marien B. Narendraprasad Reddy Freija De Vleeschouwer Steven Goderis Prof. Kristof Van Hecke Prof. Guido Verniest |
| Affiliation: | 1. Research Group of Organic Chemistry (ORGC), Department of Chemistry and Department of Bio-engineering Sciences, Faculty of Science and Bio-engineering Sciences, Vrije Universiteit Brussel (VUB), Brussels, Belgium;2. Research Group of General Chemistry (ALGC), VUB, Belgium;3. Research Group of Analytical, Environmental and Geochemistry (AMGC), VUB, Belgium;4. Department of Chemistry, Ghent University, Ghent, Belgium;5. Janssen Pharmaceutical Companies of Johnson & Johnson, PDMS-AD, Beerse, Belgium |
| Abstract: | An efficient metal‐free cascade reaction between 1‐dibromovinyl‐2‐nitro‐substituted arenes and secondary amines results in the formation of polycyclic pseudoindoxyls in a single step. The reaction mechanism leading to these fused ring systems was investigated, and is believed to involve the initial formation of nitroarylated ynamines/ynamides. These intermediates cycloisomerize towards N‐alkenyl‐tethered 2‐aminoisatogens via a carbene intermediate as demonstrated by QTAIM (quantum theory of atoms in molecules) and ELF (electron localization function) analysis. A subsequent intramolecular dipolar cycloaddition afforded the title compounds. |
| Keywords: | cycloaddition domino reactions nitrogen heterocycles ynamides ynamines |