Continuous Flow Electrochemistry Unlocks Broadly Applicable Arene C─H Amination

Abstract The direct C─H amination of arenes is a powerful strategy for synthesizing arylamines, yet existing methods often suffer from limited substrate scope, poor selectivity, or scalability issues, particularly for electron‐deficient arenes. Here, we introduce a continuous flow electrochemical C─H amination via a pyridination‐aminolysis sequence, enabling the efficient functionalization of arenes with diverse electronic properties. The method operates under continuous flow electrochemical conditions, avoiding the need for divided cells, strong chemical oxidants, or homogeneous transition‐metal catalysts. The broad substrate scope includes a wide range of electron‐rich, electron‐deficient, and halogenated arenes, as well as heterocycles, demonstrating excellent functional group tolerance. Furthermore, the process is readily scalable, as shown by a 4‐day continuous operation in parallel microreactors, producing over 100 grams of aniline product with high efficiency. This study highlights the potential of continuous‐flow electrochemistry as a versatile and practical platform for sustainable C─H functionalization in organic synthesis.