Easy access to polyhalogenated biaryls: regioselective (di)halogenation of hypervalent bromines and chlorines.

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.