Transition‐Metal‐Free Selective C−H Benzylation of Tertiary Arylamines by a Dearomatization‐Aromatization Sequence

Due to the significance of hybrid systems in drug discovery, there is an urgent need to assemble multiple biologically active ingredients into a single molecule. Here, we report a general transition‐metal‐free selective C−H benzylation of tertiary arylamines in good to excellent yields with a broad substrate scope and high functional‐group tolerance under mild conditions. Besides arylamines, some other benzene derivatives also readily furnished the corresponding diaryl methane derivatives with this protocol. A series of control experiments and theoretical calculations indicated that this transition‐metal‐free reaction is a dearomatization‐aromatization process.