Chemoselective Synthesis of Biaryls and Diaryl Sulfones via Solvent-Controlled Metal-Catalyzed S–N Bond Cleavage

Here, we first report a direct strategy for the synthesis of diaryl sulfones and biaryls from <i>N</i>,<i>N</i>-ditert-butyl-oxycarbonylsulfonamide and arylboronic acids via selective S-N bond cleavage. This method proceeds with Ni-Pd-catalyzed desulfurylative Suzuki-Miyaura cross-coupling and tandem conversion with sulfonylation, utilizing activated sulfonamides as a convenient SO₂ source. The corresponding diaryl sulfones and biaryls can be achieved in good yields under different solvent conditions. Simultaneously, the realization of the coupling of SO₂ gas and arylboronic acids to diaryl sulfones is identified as a reasonable explanation for the reaction mechanism of this strategy. Despite the inherent challenge of S-N bond cleavage, this method provides a direct approach for bench-stable sulfonamides to produce valuable sulfones and biaryl motifs.