Aniline and its derivatives, each containing one or more aromatic C(sp²)−N bonds, play a vital role as precursors or transitional materials in the synthesis of fluorescent molecules, pharmaceuticals, agricultural chemicals, rubber processing chemicals, organic dyes, pigments, and polymers. These products have a significant impact on human life. Among them, acetaminophen is the readily accessible over-the-counter analgesic, phenylenediamines and diphenylamine primarily function as the rubber antioxidant, and also the synthetic intermediate of pigments and pesticides, and fluoroaniline compounds are precursors for pharmaceutical molecules and electrode materials, and also serve as the marker in metabolism studies. Moreover, one or more aromatic C(sp²)−N bonds may be found in several currently available best-selling medication molecules, including Humira, Lenalidomide, Ibutinib, and Apixaban. Consequently, the amination of arenes has remained a significant focus in the field of organic synthetic methodology. At present, to achieve amination of arenes, the nitration-hydrogenation procedure, in which an electrophilic substitution reaction takes place between an arene and a nitration reagent (e.g. HNO₃/H₂SO₄) yielding a nitro-substituted arene, to be converted into the corresponding amino-substituted arene via catalytic hydrogenation, Bechamp method, or Zinin method, is widely adopted in laboratory and industrial syntheses. However, the intermedial nitro compounds bear potential toxicity, and the introduction and reduction of the nitro group consume excessive nitration reagents and reductants, which are far from the atomic economy and may produce a large amount of polluting waste. Additionally, some complex substrates may not tolerate the use of strong acids with high concentrations in the nitration step.

Recently, Youai Qiu’s group discussed the common mechanism manifolds of electrochemical aromatic C(sp²)-H amination reactions, combed through examples of reactions classified with the type of amine sources, and provided insights into the prospects and challenges in this field. Relevant achievements were published in Chin. J. Org. Chem., 2024, DOI: 10.6023/cjoc202310033.