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Updated: Jun 6, 2025

Preparation of Stable Bicyclic Aziridinium Ions and Their Ring-Opening for the Synthesis of Azaheterocycles
Published on: August 22, 2018
Nucleophilic Amination of Aryl Halides with an Azanide Surrogate
Bradley D Cooper1, Thomas D Harris1, Ethan R X Lim1
1Department of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK.
Abstract:
We report the development of an azanide (-NH2) surrogate which enables the facile conversion of electron-deficient (hetero)aryl halides into primary N-aryl amines under transition-metal-free conditions. The designed amidine reagent is easy to prepare, bench stable, and undergoes facile N-arylation under basic conditions at 40 °C. Intermediate N-aryl amidines are readily cleaved to form N-aryl amines in situ through hydrolysis or base-promoted elimination. The developed surrogate is a safer and more selective alternative to existing anionic N-nucleophiles, such as alkali metal amides or azide salts.
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