Nondirected Ortho\nC–H Arylation for One-Pot\nSynthesis of Biaryl Scaffolds via In Situ Generated Mixed Acetal

Herein, we introduce a mild and efficient method for\nsynthesizing\naniline biaryls and unsymmetrical phenol biaryls through iodine-catalyzed\ncoupling of quinone imine ketals (QIKs)/quinonemonoacetals (QMAs)\nand <i>β</i>-naphthols. This approach allows for the\nunusual formation of ortho-substituted anilines and phenols, valuable\nin pharmaceuticals and advanced materials but typically difficult\nto produce. Our method achieves high <i>ortho</i>-selectivity\nwithout needing transition metals or external/internal templates.\nThe process involves a [3,3] sigmatropic rearrangement of the <i>in situ</i> generated mixed acetal, which is the key intermediate.\nNotable features include scalability, broad functional group tolerance,\nand late-stage derivatization of natural products using a cost-effective,\nair-tolerant catalytic system, eliminating the need for hazardous\ncatalysts.