Catalytic Methods for Aromatic C–H Amination: An Ideal Strategy for Nitrogen-Based Functional Molecules

Abstract

Transformations of aromatic compounds into the corresponding amines, amides, and imides through carbon–hydrogen (C–H) bond functionalization represent one of the most step- and atom-economical methods for the synthesis of arylamine compounds. Because arylamines are privileged structures in materials- and biology-oriented functional molecules, the development of novel and efficient synthetic methods for aromatic C–H amination has received significant attention from a wide range of research fields including materials and pharmaceuticals. This review covers recent advances in catalytic aromatic C–H amination reactions. An array of recently developed new reactions are categorized by the nature of aromatic substrates: (1) 5-membered heteroarenes, (2) arenes having a nitrogen moiety in the molecule (intramolecular C–H amination), (3) arenes having a directing group, (4) simple arenes with excess amounts, and (5) simple arenes as the limiting reagents.

Cu-Catalyzed aromatic C–H imidation with N-fluorobenzenesulfonimide: mechanistic details and predictive models

“…Indeed, the use of C–H amination 11–16 methods allow for direct access to the desired C–N functionality in a vast range of hydrocarbons and are cost-effective and environmentally friendly. 17–19 A pertinent example is the recent breakthrough by Nicewicz and coworkers utilizing organic photoredox catalysis to functionalize arene substrates with N-heterocycles and ammonium salts.…”

Direct Aryl C−H Amination with Primary Amines Using Organic Photoredox Catalysis

“…[9–12] Significant challenges exist for C–N couplings using aliphatic amines, since many strategies for functionalization of these substrates involve C–C bond construction adjacent to the nitrogen atom. [13–16] Accordingly, C–H amination of arenes with aliphatic amines has been demonstrated only in select examples (Scheme 1).…”

Non-Deprotonative Primary and Secondary Amination of (Hetero)Arylmetals

“…Recently, a number of direct catalytic C–H amination methods have emerged that usually do not require complex optimization. 4 Although these methods represent a welcome new direction that improves overall efficiency and atom-economy, lingering issues with regio- and chemoselectivity must be adequately addressed before this strategy can be routinely and reliably deployed.…”