Selective C–S/C–O Bond Formation toward Biaryl Sulfones and Sulfinate Esters Involved with Cyclic Diaryliodoniums

Abstract Biaryl sulfones and sulfinate esters are prevalent structural motifs in pharmaceuticals and functional materials, yet divergent synthetic strategies that enable selective formation of either C–S or C–O bonds from readily available diaryliodoniums and sulfinates remain under explored. Herein, we report a condition-controlled divergent ring-opening of cyclic diaryliodonium salts with sodium sulfinates. Under metal-free heating conditions in DMSO, the reaction proceeds via selective C–S bond formation to furnish 28 biaryl sulfone derivatives with yields up to 94%. In the presence of a copper catalyst, the selectivity is switched to favor C–O bond formation, delivering biaryl sulfinate esters. This protocol not only enriches the synthetic toolkit for biaryl sulfone scaffolds but also offers a facile new route toward biaryl sulfinate esters.