I(III)-Mediated Arene C-H Amination using (Hetero)Aryl Nucleophiles

Abstract

Herein, we report the metal-free oxidative C-H amination of arenes via a heterocyclic group transfer reaction from an I(III) N-HVI reagent. N-heterocycles serve as an oxidatively masked amine nucleophile and the resulting N-aryl pyridinium salts are inert to further oxidation. The products provide a versatile handle to access valuable aryl amine derivatives. The reaction proceeds under mild conditions and has good scope of both arene and N-heterocycle.

I(III)-Mediated Arene C–H Amination Using (Hetero)Aryl Nucleophiles

“…Herein, we report the metal-free oxidative amination of electron-rich aromatics via HGT with I(III) N-HVIs. 29 The reaction proceeds under mild, operationally simple conditions and was demonstrated on seven arene derivatives and nine electronically diverse N-heterocycles. The resulting N-aryl (hetero)arylonium salts can be subsequently functionalized, or we demonstrate efficient cleavage to reveal the free amine.…”

“…Herein, we report the metal-free oxidative amination of electron-rich aromatics via HGT with I­(III) N -HVIs . The reaction proceeds under mild, operationally simple conditions and was demonstrated on seven arene derivatives and nine electronically diverse N-heterocycles.…”

Site-Selective Electrochemical Arene C–H Amination

“…Traditional methods for nondirected aromatic C− H amination rely on a sequential nitration 3 /reduction/ alkylation process, which suffers from limitations in site selectivity and substrate compatibility. Consequently, researchers have explored several alternative approaches utilizing transition metal catalysis, 4,5,6a stoichiometric reactive reagents, 7 and, in the past decade, novel photocatalytic methods 8,9 to enhance selectivity and expand substrate scope.…”