Meta-OTf-Substituted Diaryliodonium Salts Enabled Aryne 1,2,2'-Trifunctionalization via Thia-Fries and Aza-Claisen Rearrangements

A novel cascade reaction involving thia-Fries and aza-Claisen rearrangements has been developed using meta-trifluoromethanesulfonate-substituted diaryliodonium salts, featuring the generation of aryne intermediates. In contrast to previously reported methods that achieve trisubstitution on a single aryne ring, our approach enables 1,2,2'-trisubstitution across two distinct aromatic rings of diarylamines. The reaction efficiently forms C-N, C-S, and C-C bonds at adjacent positions on each aromatic ring in a sequential manner.