Electrochemical Benzylic C–H Sulfation beyond the O‐Sulfonation Limitation

Direct C–H sulfation represents a valuable transformation for the synthesis of organosulfates. However, it has been challenging to achieve owing to the presence of multiple C–H bonds with comparable strengths and steric environments. Current methods for producing organosulfates primarily rely on O‐sulfonation, which limits their applicability to hydroxyl‐containing compounds. Herein, we report a practical and cost‐efficient method for the electrochemical sulfation of benzylic C–H bonds. This reaction avoids the need for strong oxidants, demonstrating broad substrate scope, excellent chemoselectivity and site selectivity. The orthogonal reactivity of this protocol is particularly evident in the transformation of alcohol substrates.