Herein, we introduce a mild and efficient method for synthesizing aniline biaryls and unsymmetrical phenol biaryls through iodine-catalyzed coupling of quinone imine ketals (QIKs)/quinonemonoacetals (QMAs) and β-naphthols. This approach allows for the unusual formation of ortho-substituted anilines and phenols, valuable in pharmaceuticals and advanced materials but typically difficult to produce. Our method achieves high ortho-selectivity without needing transition metals or external/internal templates. The process involves a [3,3] sigmatropic rearrangement of the in situ generated mixed acetal, which is the key intermediate. Notable features include scalability, broad functional group tolerance, and late-stage derivatization of natural products using a cost-effective, air-tolerant catalytic system, eliminating the need for hazardous catalysts.