Nucleophilic Amination of Aryl Halides with an Azanide Surrogate

We report the development of an azanide (−NH2) surrogate which enables the facile conversion of (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.