Enhanced Reactivity of [Hydroxy(tosyloxy)iodo]benzene in Fluoroalcohol Media. Efficient Direct Synthesis of Thienyl(aryl)iodonium Salts

In this manuscript, we report clear evidence for the generation of aromatic cation radicals produced by using [hydroxy(tosyloxy) iodo] benzene (HTIB) in fluoroalcohol solvents such as 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP). The single-electron-transfer (SET) oxidation ability of HTIB to give cation radicals was first established by ESR and UV measurements. The reaction was broadly applied to various thiophenes, and unique thienyliodonium salts were directly synthesized by this method in excellent yields without the production of any harmful byproducts.