Reactivity of Hydroxy- and Aquo( hydroxy)-l3-iodane- Crown Ether Complexes

We have designed a series of hydroxy(aryl)-(3)-iodane-[18]crown-6 complexes, prepared from the corresponding iodosylbenzene derivatives and superacids in the presence of [18]crown-6, and have investigated their reactivities in aqueous media. These activated iodosylbenzene monomers are all non-hygroscopic shelf-storable reagents, but they maintain high oxidizing ability in water. The complexes are effective for the oxidation of phenols, sulfides, olefins, silyl enol ethers, and alkyl(trifluoro)borates under mild conditions. Furthermore, hydroxy-(3)-iodane-[18]crown-6 complexes serve as efficient progenitors for the synthesis of diaryl-, vinyl-, and alkynyl-(3)-iodanes in water. Other less polar organic solvents, such as methanol, acetonitrile, and dichloromethane, are also usable in some cases.