Electrochemical Biomimetic Iron‐Catalyzed Benzylic C─H Bonds Hydroxylation

ABSTRACT Electrochemical synthesis has attracted considerable attention as a green synthetic technology in recent years, particularly in the domain of selective oxidation and reduction, which represents a significant yet ongoing challenge in the field. This protocol presents a biomimetic iron‐catalyzed electrochemical benzylic C─H bond hydroxylation through a water activation strategy, where in situ‐generated high‐valent iron‐oxo species mediate, enabling efficient and highly selective benzylic hydroxylation. The method exhibits excellent selectivity and broad functional group compatibility, applicable to primary, secondary, and tertiary benzylic C─H bonds, and suitable for late‐stage modification of bioactive molecules. Mechanistic studies highlight the efficacy of a dual‐control approach combining indirect electrolysis with a detached reaction layer to prevent direct substrate oxidation. This method offers a practical and green route to the synthesis of diverse benzyl alcohols.