title: Reactivity of hydroxy- and aquo(hydroxy)-λ3-iodane-crown ether complexes.
abstract: We have designed a series of hydroxy(aryl)-λ(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-λ(3)-iodane-[18]crown-6 complexes serve as efficient progenitors for the synthesis of diaryl-, vinyl-, and alkynyl-λ(3)-iodanes in water. Other less polar organic solvents, such as methanol, acetonitrile, and dichloromethane, are also usable in some cases.
authors.affiliation: Graduate School of Pharmaceutical Sciences, University of Tokushima, 1-78 Shomachi, Tokushima 770-8505 (Japan). kmiya@tokushima-u.ac.jp.
authors.forename: Kazunori
authors.initials: K
authors.lastname: Miyamoto
authors.forename: Yukie
authors.initials: Y
authors.lastname: Yokota
authors.forename: Takashi
authors.initials: T
authors.lastname: Suefuji
authors.forename: Kentaro
authors.initials: K
authors.lastname: Yamaguchi
authors.forename: Tomoyuki
authors.initials: T
authors.lastname: Ozawa
authors.forename: Masahito
authors.initials: M
authors.lastname: Ochiai
mesh_terms: D043844:Crown Ethers / Q000737:chemistry*; D007455:Iodine / Q000737:chemistry*; D007462:Iodobenzenes / Q000737:chemistry*; D008958:Models, Molecular; D010084:Oxidation-Reduction
chemical_list: D043844:Crown Ethers; D007462:Iodobenzenes; D007455:Iodine; C037276:iodosobenzene
keywords: crown ethers; hypervalent compounds; iodine; oxidation; supramolecules