Synthesis of <i>o</i>‑Aryloxy Triarylsulfonium Salts via Aryne Insertion into Diaryl Sulfoxides

The aryne insertion into “SO” bond has been validated recently. This technology is elusively applied to the synthesis of thioethers. In contrast to the reported cases, the reaction described furnished <i>o</i>-aryloxy triarylsulfonium salts, in lieu of thioethers, in good to excellent yields. The reaction is also featured by its exquisite regioselectivity, broad substrate scope, and mild conditions (25 °C). Preliminary mechanistic studies suggest that the reaction probably proceeds in a sequential [2 + 2] cycloaddtion/<i>O</i>-arylation/protonation pathway