meta-Substituted Diaryliodonium Salts Enabled Aryne 1,2,4′-Trifunctionalization

A novel 1,2,4′-trifunctionalization of arynes was accomplished using meta-substituted diaryliodonium salts through a unique [5,5]-sigmatropic shift followed by a thia-Fries rearrangement. This cascade transformation enables the sequential formation of both C–N and C–S bonds, while also achieving the synthetically challenging para-selective C–C bond on the non-aryne aromatic ring.