V–Catalyzed Direct Ortho‐Aminomethylation of Phenols

A strategy for cross‐dehydrogenative C(sp2)‐C(sp3) coupling was developed by direct and highly selective V‐catalyzed ortho‐aminomethylation of phenol with aniline derivatives. A series of aminomethylphenol compounds were obtained in moderate to good yields under mild reaction conditions and with a broad substrate scope. A possible radical mechanism was proposed, and it was found that the coordination of phenolic hydroxyl groups with V⁵⁺ was crucial for the effective activation of the ortho position.