Condition-Regulated Regiodivergent Synthesis of Biaryl Sulfones via Sulfonylation of Diaryl λ 3 -Bromanes and Chloranes

A regiodivergent sulfonylation of cyclic diaryl λ³-bromanes and λ³-chloranes has been developed, enabling the selective synthesis of biaryl sulfones. Under base-mediated conditions, meta-selective sulfonylation proceeds via aryne intermediates, while copper catalysis switches the pathway to ortho-selective sulfonylation. Both strategies afford diverse sulfones in moderate to excellent yields. Gram-scale reactions highlights its potential for practical applications. This protocol demonstrates the distinct reactivity of diaryl λ³-bromanes and λ³-chloranes and offers a practical, scalable approach to regiodivergent sulfone synthesis.