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Metal‐Free Cyclization of ortho ‐Nitroaryl Ynamides and Ynamines towards Spiropseudoindoxyls
Author(s) -
Marien Niels,
Reddy B. Narendraprasad,
De Vleeschouwer Freija,
Goderis Steven,
Van Hecke Kristof,
Verniest Guido
Publication year - 2018
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201800340
Subject(s) - intramolecular force , chemistry , cycloaddition , carbene , ring (chemistry) , molecule , nitro , metal , computational chemistry , photochemistry , medicinal chemistry , stereochemistry , organic chemistry , catalysis , alkyl
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.