Article Synopsis
- A new method for converting nitroarenes into specialized compounds called 2-amino-3-azepines is introduced, involving a specific organophosphorus catalyst and a mild reductant.
- This process includes creating aryl nitrenes through the removal of oxygen, which are then transformed by adding amines and expanding their ring structures.
- Finally, these intermediates undergo a reaction with acyl electrophiles that leads to a rearrangement, resulting in the formation of aromatic products like 2-aminoanilides and benzimidazoles.
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Article Abstract
A synthetic method for the reductive transformation of nitroarenes into -aminated and -annulated products is reported. The method operates via the exhaustive deoxygenation of nitroarenes by an organophosphorus catalyst and a mild terminal reductant to access aryl nitrenes, which after ring expansion, are trapped by amine nucleophiles to give dearomatized 2-amino-3-azepines. Treatment of these ring-expanded intermediates with acyl electrophiles triggers 6π electrocyclization to extrude the nitrogen atom and restore aromaticity of the phenyl ring, which delivers via C-H functionalization 2-aminoanilide and benzimidazole products.
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| http://www.ncbi.nlm.nih.gov/pmc/articles/PMC9839621 | PMC |
| http://dx.doi.org/10.1021/jacs.2c12450 | DOI Listing |
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Tandem C/N-Difunctionalization of Nitroarenes: Reductive Amination and Annulation by a Ring Expansion/Contraction Sequence.
J Am Chem Soc
January 2023
Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States.
Article Synopsis
- A new method for converting nitroarenes into specialized compounds called 2-amino-3-azepines is introduced, involving a specific organophosphorus catalyst and a mild reductant.
- This process includes creating aryl nitrenes through the removal of oxygen, which are then transformed by adding amines and expanding their ring structures.
- Finally, these intermediates undergo a reaction with acyl electrophiles that leads to a rearrangement, resulting in the formation of aromatic products like 2-aminoanilides and benzimidazoles.