Preparation and Structure of Meta-Hydroxy-Substituted Aryliodonium Salts: New Structural Type of Phenol-Derived Hypervalent Iodine Compounds

The previously unknown meta-hydroxy-substituted aryliodonium salts were prepared by a two-step one-pot synthesis based on the reaction of 3-acetoxy-1-[(diacetoxy)iodo]arenes with arylboronic acids, involving the initial formation of 3-acetoxyphenyl(phenyl)iodonium salts and followed by deacetylation of the intermediate product in the presence of trifluoromethanesulfonic acid. The procedure works well with halogen-, methyl-, methoxycarbonyl-, or methoxy-substituted arylboronic acids as well as naphthalenylboronic acids, phenanthren-9-ylboronic acid, and thiophen-3-ylboronic acid. The structure of 3-hydroxyphenyl(phenyl)iodonium triflate was confirmed by single-crystal X-ray crystallography.