Synthesis of 4‐(Benzylideneamino)phenol Derivatives Using a Hypervalent Iodine‐Mediated Approach

Abstract The widespread utility of imines in pharmaceutical and materials science has spurred continuous methodological innovations in their synthesis; however, persistent challenges remain in achieving both mild reaction conditions and broad substrate compatibility. This work reports a novel hypervalent iodine‐mediated dearomatization strategy for the synthesis of 4‐(benzylideneamino)phenol derivatives via C(aryl)─NH 2 bond cleavage. The metal‐free protocol achieves unprecedented 15 N‐directed transfer from alkyl amines to aromatic systems while preserving exceptional functional group compatibility. The synthetic utility is further demonstrated by the successful preparation of challenging secondary amines and 6‐hydroxyquinoline derivatives under ambient conditions. Mechanistic investigations, including isotopic labeling and DFT calculations, reveal that 4‐aminocyclohexa‐2,5‐dien‐1‐one cation species serve as key intermediates. This atom‐economical approach establishes a simple, metal‐free platform for constructing bioactive nitrogen architectures, particularly offering streamlined access to 15 N‐labeled anilines with potential applications in drug discovery and chemical biology.