type: misc

label: url

en: 超原子価スルホニルイミノブロマン(III)による不活性アルカンの高位置選択的アミノ化反応

en: Japanese Scientists in Science 2011

ja: サイエンスに載った日本人研究者


en: Organocatalytic Oxidative Cleavage of Carbon-Carbon Double Bonds

ja: 有機触媒による酸化的炭素ー炭素二重結合切断反応

en: Oxidative cleavage of carbon-carbon double bonds to carbonyl compounds is an essential operation in organic synthesis. Ozonolysis is generally accepted as the standard method for this direct transformation. However, its utility is often limited by safety concerns. Use of high-valent oxometals such as RuO4, OsO4, and MeReO3 in combination with a number of oxygen donors as stoichiometric oxidants is suitable for the oxidative catalytic cleavage of olefins, but they are expensive and/or toxic. Therefore, the development of a safe and environmentally friendly procedure for the cleavage of carbon-carbon double bonds is highly desirable. In this review, we report a safe, environment-friendly, and heavy metal-free ozonolysis of olefins, which involves activated iodosylbenzene monomers, hydroxy-λ3-iodanes, as active species. Organocatalytic version of the oxidative cleavage of olefins that involves in situ generation of hypervalent aryl-λ3-iodanes as effective organocatalysts and the use of <I>m</I>-chloroperbenzoic acid as a stoichiometric terminal oxidant under metal-free conditions is described. Cyclic and acyclic olefins as well as aliphatic and aromatic alkynes were cleaved to carboxylic acids under the organocatalytic conditions.

en: Journal of Synthetic Organic Chemistry, Japan

ja: 有機合成化学協会誌


en: Stoichiometric and Catalytic Oxidation with Hypervalent Organo-λ3-iodanes

en: Isolation, characterization, and reaction of the activated iodosylbenzene monomer, hydroxy(phenyl)iodonium ion, as a complex with 18-crown-6 (18C6) are reported. The reaction of iodosylbenzene with HBF(4) in the presence of 18C6 afforded the hydroxy-lambda(3)-iodane complex PhI(OH)BF(4).18C6 as stable yellow prisms. X-ray structure analysis indicated that the close contacts between the iodine(III) and the three adjacent oxygen atoms of 18C6 will be responsible for the increased stability of the complex compared to the uncomplexed PhI(OH)BF(4). The aqua complex of the activated iodosylbenzene, PhI(OH)OTf.18C6.H(2)O, with a water molecule coordinated to iodine(III) was also prepared. These crown ether complexes are highly reactive and serve as versatile stoichiometric oxidants, especially in water. Thus, the complexes undergo oxidative transformations of a variety of functional groups such as olefins, alkynes, enones, silyl enol ethers, sulfides, and phenols under mild conditions. The latter part reports on the iodobenzene-catalyzed alpha-oxidation of ketones, in which diacyloxy(phenyl)-lambda(3)-iodanes generated in situ act as real oxidants of ketones and m-chloroperbenzoic acid (m-CPBA) serves as a terminal oxidant. The oxidation of a ketone with m-CPBA in acetic acid in the presence of a catalytic amount of iodobenzene, BF(3)-Et(2)O, and water at room temperature affords an alpha-acetoxy ketone in good yield. It is noted that the use of water and BF(3)-Et(2)O is crucial to the success of this alpha-acetoxylation.

en: Chemical Record

ja: Chemical Record


en: Intermolecular Hypervalent I(III)-O Interactions: A New Driving Force for Complexation of Crown Ethers

en: Coordination Chemistry Reviews

ja: Coordination Chemistry Reviews


en: オレフィンのSN2反応:認知まで15年

ja: オレフィンのSN2反応:認知まで15年

en: FIU Letters

ja: FIU Letters


en: Nucleophilic Vinylic Substitutions of λ3-Vinyliodanes

en: Journal of Organometallic Chemistry

ja: Journal of Organometallic Chemistry


en: 2分子求核置換反応 (SN2反応)が変わる! 5配位炭素化合物の合成とオレフィンのSN2反応

en: 化学

ja: 化学


en: Reaction of λ3-Vinyliodanes: Generation and Alkylidene-Transfer of Monocarbonyl Iodonium Ylides

ja: Journal of Synthetic Organic Chemistry, Japan


en: ヨウ素資源の活用 --- 超原子価有機ヨウ素化合物の合成と反応

ja: ヨウ素資源の活用 --- 超原子価有機ヨウ素化合物の合成と反応

en: TCIメール

ja: TCIメール


en: アルキリデンカルベンの生成と有機合成

ja: アルキリデンカルベンの生成と有機合成

en: Farumashia

ja: ファルマシア


en: Synthesis reaction of Hypervalent Alkylperoxyiodance and Single-Crystal X-Ray Analysis

en: The Rigaku-Denki Journal

ja: The Rigaku-Denki Journal