Intramolecular Aryl Migration of Diaryliodonium Salts: Access to ortho-Iodo Diaryl Ethers

By using vicinal trifluoromethanesulfonate-substituted diaryliodonium salts, a novel approach was developed for the synthesis of ortho-iodo diaryl ethers by intramolecular aryl migration. The reaction conditions are mild with a broad substrate scope. Mechanistic insight suggests a sulfonyl-directed nucleophilic aromatic substitution pathway. Additionally, the product ortho-iodo diaryl ethers serve as versatile synthons as demonstrated with several coupling reactions. Furthermore, a useful thyroxine analogue of the 3-iodo-L-thyronine (3-T-1) derivative was synthesized by this aryl migration procedure.