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 N,N-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.