Abstract
Polyhalogenated biaryls are unique motifs offering untapped potential as versatile building blocks for the expedient synthesis of complex biaryl compounds. Overcoming the limitations of conventional syntheses, we introduce a novel, metal-free, operationally simple and one-pot approach to regioselectively (di)halogenate biaryl compounds under mild conditions using cyclic biaryl hypervalent bromine and chlorine substrates as masked arynes. Through chemoselective post-functionalizations, these valuable products can expand the toolbox for synthesizing biaryl-containing scaffolds, addressing a critical gap in the field.