研究者詳細 - 宮本　和範

A conceptually distinct, modern strategy for Baeyer-Villiger oxidation (BVO) was developed. Our novel method involves initial hydration of water to carbonyl compounds, followed by ligand exchange of hypervalent arylbromane on bromane(III) with the resulting hydrate, yielding a new type of activated Criegee intermediate. The intermediate undergoes BV rearrangement and produces an ester via facile reductive elimination of arylbromanyl group, because of the hypernucleofugality. The novel strategy makes it possible to induce selectively the BV rearrangement of straight chain primary aliphatic as well as aromatic aldehydes, which is missing in the classical BVO: for instance, octanal and benzaldehyde afforded rearranged formate esters with high selectivity (>95%) under our conditions, while the attempted their classical BVO produced only carboxylic acids. This firmly establishes the powerful nature of new methodology for BVO.

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Imination of Sulfides and Sulfoxides with Sulfonylimino-λ3-Bromane under Mild, Metal-Free Conditions.

宮本和範

Chem.Eur.J. 16 8713 - 8718 2010年

Hypervalent λ3-Bromane Strategy for Baeyer-Villiger Oxidation : SelectiveTransformation of Primary Aliphatic and Aromatic Aldehydes to Formates, Which is Missing in the Classical Baeyer-Villiger Oxidation.

宮本和範

J.Am.Chem.Soc. 132 9236 - 9239 2010年

Hypervalent N-Sulfonylimino-λ3-bromane : Active Nitrenoid Species at Ambient Temperature under Metal-free Conditions

宮本和範

Chem.Commun. 46 511 - 521 2010年

Final formation of cyclic-vinyl cations : formation of cyclopentenyl cations.

宮本和範

Kagaku 65 72 - 73 2010年

Effects of stereochemistry and β-substituents on the rates of vinylic SN2 reaction of hypervalent vinyl(phenyl)-λ3-iodanes with tetrabutylammonium halides.

宮本和範

Tetrahedron 66 5819 - 5826 2010年

Difluoro-λ3-bromane-Induced Hofmann Rearrangement of Sulfonamides : Synthesis of Sulfamoyl Fluorides.

宮本和範

J.Am.Chem.Soc. 131 8392 - 8393 2009年

Oxidation of Benzyl Alcohols with Difluoro(aryl)-λ3-bromane:Formation of Benzyl Fluoromethyl Ethers via Oxidative Rearrangement.

宮本和範

Tetrahedron Lett. 50 4792 - 4795 2009年

Iodomesitylene-Catalyzed Oxidative Cleavage of Carbon-Carbon Double and Triple Bonds Using m-Chloroperbenzoic Acid as a Terminal Oxidant

宮本和範

J. Am. Chem. Soc. 131 1382 - 1383 2009年

Facile Generation of a Strained Cyclic Vinyl Cation by Thermal Solvolysis of Cyclopent-1-enyl-λ3-bromanes. Angew.

宮本和範

Chem.Int.Ed. 48 8931 - 8934 2009年

Catalytic version of and reuse in hypervalent organo-λ3- and -λ5-iodane oxidation

Ochiai M., Miyamoto K.

European Journal of Organic Chemistry （ 25 ） 4229 - 4239 2008年09月

ISSN 1434193X

Hypervalent organoiodanes are one of the most valuable classes of oxidants for use in oxidative transformations of various kinds of functionalities in modern organic synthesis. This microreview provides an overview of the recently developed aryl iodide-catalyzed oxidations, in which hypervalent organoiodanes(III and V) generated in situ serve as the actual oxidants. We also summarize recent attempts to improve the efficiency of recyclable hypervalent organoiodanes in oxidations, updating Togo's and Sakuratani's 2002 review. © Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

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Catalytic Version of and Reuse in Hypervalent Organo-λ^3- and λ^5-Iodane Oxidation.

落合正仁, 宮本和範

Eur.J.Org.Chem. 4229 - 4239 2008年

三価のブロマニル超脱離基を活用するシクロペンテニルカチオン発生反応

宮本和範, 大久保琢爾, 落合正仁

基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）（基礎有機化学会（基礎有機化学連合討論会）） 2008 341 - 341 2008年

超脱離基である三価の超原子価ヨウ素置換基を有するビニル-λ3-ヨーダンは、SN1機構で種々のビニルカチオンを発生することが知られているが、シクロペンテニル-λ3-ヨーダンの加溶媒分解反応では、シクロペンテニルカチオンは発生しない。我々はこれを遥かに凌ぐ脱離能を有する三価の超原子価臭素置換基を導入したシクロペンテニル-λ3-ブロマンを設計・合成し、その加溶媒分解反応を実施した。興味深いことに、本反応は緩和な条件下にSN1機構で進行し、シクロペンテニルカチオンが生成している。

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イミノブロマンのトランスイミノ化反応：イミノヨーダンの合成

中野愛子, 吉村祥, 金秋鷹雄, 宮本和範, 落合正仁

反応と合成の進歩シンポジウム発表要旨概要（日本薬学会化学系薬学部会） 34 24 - 24 2008年

Iminoiodanes serve as excellent nitrenoid progenitors in the aziridination of olefins and in the C-H amidation of alkanes under transition metal-catalyzed conditions. The methodology for synthesis of the iminoiodanes is, however, very limited and all of the methods reported rely on ligand exchange on iodine of aryliodanes. We report the first example of transimidations yielding sulfonyliminoiodanes, which involves an imido transfer from iminobromane to the iodine atom of iodobenzenes at room temperature under metal-free conditions. Rate dependence on the concentration of iodobenzene suggests a bimolecular nitrenoid transition state, involving a rate-limiting nucleophilic attack of iodobenzene on the negatively charged nitrogen of sulfonyliminobromane. Hammett plot indicates large buildup of positive charge on the iodine of iodobenzenes in the transition state.

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臭素イリドのトランスイリド化とアリール化反応

多田教浩, 岡田拓也, 曽田篤志, 宮本和範, 落合正仁

反応と合成の進歩シンポジウム発表要旨概要（日本薬学会化学系薬学部会） 33 78 - 78 2007年

Stable bromonium ylides have been synthesized and structurally characterized for the first time. The bromonium ylides selectively undergo transfer of the aryl group to nitrogen heterocycles. This is in a marked contrast to the reaction of the iodonium ylides, which produces pyridinium ylides through transylidations. Intermolecular transylidation between halonium ylides under thermal and catalytic conditions, which makes it possible to synthesize a hitherto unknown kind of chloronium ylides as well as a variety of bromonium and iodonium ylides, was developed. The thermal transylidations of bromonium to iodonium ylides probably involve generation of a reactive carbene. Compared to the bromonium and iodonium ylides, the chloronium ylide serves as a much better progenitor for generation of carbenes. A greater leaving group ability of the chroranyl(III) and bromanyl(III) groups compared to that of the iodanyl(III) group seems to be responsible for the observed differences in reactivity.

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One-Pot Regioselective Synthesis of Chromany】(pheny】)-λ^3・iodanes: Tandem Oxidative Cyclization and λ^3・Iodanation of 3・Phenypropanols

宮本和範

Org. Lett. 9 1995 - 1998 2007年

One-Pot Regioselective Synthesis of Chromanyl(phenyl)-λ^3-iodanes:Tandem Oxidative Cyclization andλ^3-Iodanation of 3-Phenvlpropanols

宮本和範

Org. Lett. 9 1995 - 1998 2007年

One-Pot Regioselective Synthesis of Chromanyl (phenyl)-λ^3-iodanes: Tandem Oxidative Cyclization and λ^3-Iodanation of 3-Phenylpropanols

宮本和範

Org. Lett. 9 1995 - 1998 2007年

シルバーテクノロジー：銀Ｚーエンチオラートの合成と反応

廣部雅也, 宮本和範, 落合正仁

反応と合成の進歩シンポジウム発表要旨概要（日本薬学会化学系薬学部会） 32 274 - 274 2006年

Reported here for the first time are the stereoselective synthesis and reaction of simple silver (Z)-enethiolates, which serve as a stabilized (Z)-enethiol storage. In contrast to labile enethiols, silver (Z)-enethiolates are stable even in solutions, and their isolation and purification are very simple. The method for synthesis of silver (Z)-enethiolates involves an unusual vinylic SN2 reaction of (E)-vinyliodane(III) with thiobenzamides yielding the inverted (Z)-S-vinylthioimidonium salts, followed by their regioselective C-S bond cleavage with silver acetate. Alkylation, arylation, and Michael addition of silver (Z)-enethiolates yielding (Z)-vinyl sulfides was dramatically accelerated by the addition of Bu4NI (LiI), which probably generates reactive ammonium (Z)-enethiolates with an increased nucleophilicity.

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エチニルヨーダン—クラウンエーテル錯体の合成とその反応

宮本和範, 末藤孝志, 落合正仁

反応と合成の進歩シンポジウム発表要旨概要（日本薬学会化学系薬学部会） 29 24 - 25 2003年

エチニル-l3-ヨーダン（１）はエノラートアニオンなどの求核種に直接エチニル基を導入できる合成上特異な反応剤である。[1] 東京化成工業より既に市販されているが、問題となるのはその安定性である。室温で保存すると分解してしまうため、幅広く利用するためにはその安定性を向上させる必要がある。我々は（１）に18-クラウン-6(18C6)を作用させたところ、室温で保存できる安定な結晶として1:1錯体（２）を得ることに成功した(Scheme 1)。[2] ２つの酸素原子とσ*(I–C)軌道との間の超原子価相互作用により安定化されていることがX線結晶解析図(Figure 1)からわかる。CSI–MSやJobプロットを用いて溶液中での構造も決定した。安定性の向上が原因であると思われるが、1:1錯体（２）はエチニル化剤として極めて有用である。代表例をScheme 2に示す。いずれの場合も反応は高収率で進行し、（１）の反応性が大幅に改良された。（１）を用いると不安定なZ-ビニル-l3-ヨーダンも合成可能である。

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