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A catalytic metal‐free approach for the H/D exchange in aromatic compounds using D2O as the terminal deuterating reagent has been developed. This metal‐free protocol employs a triaryl carbenium as the mediator and showcases a wide applicability in the late‐stage deuteration of various natural products and small‐molecule drugs. Gram‐scale deuteration was successfully demonstrated with β‐Estradiol, highlighting the method‘s practicability. Detailed mechanistic insights, supported by DFT calculations, unveiled the essential role of in situ generated acidic species in this electrophilic aromatic substitution process. This newly developed method offers a sustainable and versatile alternative to traditional metal‐catalyzed H/D exchange techniques, addressing challenges such as the use of expensive metals, impurity formation, and the necessity for residual metal removal from the final products. [ABSTRACT FROM AUTHOR]

The selective oxidation of benzylic C−H bonds is a pivotal transformation in organic synthesis. Undoubtedly, achieving efficient and highly selective aerobic oxidation of methylarenes to benzaldehydes has been highly challenging due to the propensity of benzaldehyde to undergo overoxidation under typical aerobic conditions. Herein, we propose an innovative approach to address this issue by leveraging electrocatalytic processes, facilitated by ion‐pair mediators [Ph3C]+[B(C6F5)4]−. By harnessing the power of electrochemistry, we successfully demonstrated the effectiveness of our strategy, which enables the selective oxidation of benzylic C−H bonds in benzylic molecules and toluene derivatives. Notably, our approach exhibited high efficiency, excellent selectivity, and compatibility with various functional groups, underscoring the broad applicability of our methodology. [ABSTRACT FROM AUTHOR]