Marien Niels, Reddy B Narendraprasad, De Vleeschouwer Freija, Goderis Steven, Van Hecke Kristof, Verniest Guido
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), Pleinlaan 2, 1050, Brussels, Belgium.
Research Group of General Chemistry (ALGC), VUB, Belgium.
Angew Chem Int Ed Engl. 2018 May 14;57(20):5660-5664. doi: 10.1002/anie.201800340. Epub 2018 Apr 16.
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.
1-二溴乙烯基-2-硝基取代芳烃与仲胺之间高效的无金属串联反应可一步生成多环假吲哚酚。对导致这些稠环体系的反应机理进行了研究，据信该反应涉及硝基芳基化烯胺/烯酰胺的初始形成。如通过QTAIM（分子中原子的量子理论）和ELF（电子定位函数）分析所证明的，这些中间体通过卡宾中间体向N-烯基连接的2-氨基异吲哚酮环异构化。随后的分子内偶极环加成反应得到了标题化合物。
