Electrochemical Biomimetic Iron‐Catalyzed Benzylic C─H Bonds Hydroxylation

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.