meta-OTf-substituted diaryliodonium salts enabled aryne 1,2,2′-trifunctionalization via a cascade of thia-Fries and aza-Claisen rearrangements†

Abstract

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