研究者詳細 - ウヤヌク　ムハメット

その他リンク： https://pubs.rsc.org/en/content/articlelanding/2025/cc/d4cc06472k

Unraveling Alcohol Additive Effects on Hypervalent Iodine(III)-Catalyzed Asymmetric Phenolic Dearomatization: Ligand Substitution and Low-Barrier Hydrogen Bonds 査読有り国際共著

Zheng, HL; Cai, L; Lai, XY; Uyanik, M; Ishihara, K; Xue, XS

ACS CATALYSIS 15 巻 ( 1 ) 頁： 370 - 380 2024年12月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：ACS Catalysis

Despite the widespread use of hexafluoropropanol (HFIP) as a “magic” solvent or additive in organic synthesis, its fundamental mechanisms lag far behind. This study presents mechanistic insights into the puzzling alcohol additive effects observed in Ishihara’s conformationally flexible C2-symmetric iodoarene-catalyzed asymmetric phenolic dearomatization through density functional theory calculations. The results reveal that due to the “booster effect” of fluorinated alcohols, HFIP assembles a trimeric hydrogen bond cluster that displaces a ligand from the active iodine(III) catalyst and forms a low-barrier hydrogen bond with the substrate, which significantly enhances the oxidizing power of the iodine(III) center, thus facilitating the dearomatization of electron-deficient phenols. Conversely, methanol is found to promote the dearomatization of electron-rich phenols via a formally similar yet distinct mechanism, thus highlighting the unique role of HFIP as an additive. The insights gained from this investigation advance our molecular-level understanding of the synergistic interactions between catalysts and additives, potentially guiding the design of catalytic systems that exploit these effects for broader applications.

DOI： 10.1021/acscatal.4c06557

その他リンク： https://pubs.acs.org/doi/10.1021/acscatal.4c06557

Inner-Bond-Cleavage Approach to Figure-Eight Macrocycles from Planar Aromatic Hydrocarbons 査読有り国際共著国際誌 Open Access

Yoshina, R; Hirano, J; Nishimoto, E; Sakamoto, Y; Tajima, K; Minabe, S; Uyanik, M; Ishihara, K; Ikai, T; Yashima, E; Omine, T; Ishiwari, F; Saeki, A; Kim, J; Oh, J; Kim, D; Liu, GT; Yasuda, T; Shinokubo, H; Fukui, N

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146 巻 ( 43 ) 頁： 29383 - 29390 2024年9月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of the American Chemical Society

Figure-eight-shaped nonplanar π-systems adopt distinctive chiral D2-symmetric structures, which are ideal for realizing efficient circularly polarized luminescence (CPL). However, the short-step and enantioselective synthesis of figure-eight π-systems represents a considerable challenge for the conventional bottom-up synthetic strategy. Herein, we report that the oxidative cleavage of the internal double bond of a commercially available polycyclic aromatic hydrocarbon, i.e., dibenzo[g,p]chrysene (DBC), catalytically affords a figure-eight electron-accepting macrocycle, i.e., cyclobisbiphenylenecarbonyl (CBBC), with high scalability (up to 3.3 g) and excellent enantioselectivity (94% ee). This inner-bond-cleavage approach also applies to larger PAHs, affording highly distorted molecular frameworks that comprise two figure-eight subunits. Furthermore, we demonstrate that the peripheral functionalization of CBBC with carbazole afforded donor-acceptor-type emitter, which shows thermally activated delayed fluorescence and emits CPL with a g value of 1.0 × 10-2. This g value is ten times higher than those of previously reported chiral TADF-active emitters for circularly polarized organic light-emitting diodes. These results demonstrate that oxidative inner-bond cleavage is a powerful synthetic strategy for creating innovative materials that incorporate molecules with figure-eight structures.

DOI： 10.1021/jacs.4c07985

その他リンク： https://pubs.acs.org/doi/10.1021/jacs.4c07985

Oxidative Dearomative Coupling of Electron-Deficient Arenols Using Hypohalite Catalysis 査読有り

Kato, T; Sahara, N; Akagawa, S; Uyanik, M; Ishihara, K

ORGANIC LETTERS 26 巻 ( 34 ) 頁： 7255 - 7260 2024年8月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Organic Letters

We developed performant in situ hypohalite, especially hypobromite, catalysis for the oxidative dearomatization of low-reactivity electron-deficient arenols. The reaction scope encompasses inter- and intramolecular oxidative dearomative C-O, C-N, and C-C coupling reactions. Notably, using a chiral ammonium countercation, we achieved enantioselective hypobromite catalysis for oxidative dearomative coupling reactions. Mechanistic studies revealed that the reaction mechanisms might differ depending on the halide identity.

DOI： 10.1021/acs.orglett.4c02787

Hypoiodite-Catalyzed Oxidative α-C-N Coupling of Ketones with Imides and Azoles 招待有り査読有り国際誌

Tsukahara, M; Uyanik, M; Ishihara, K

ADVANCED SYNTHESIS & CATALYSIS 365 巻 ( 16 ) 頁： 2724 - 2729 2023年8月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Advanced Synthesis and Catalysis

Herein, we report a direct method for the synthesis of α-imidoketones and α-azolylketones via hypoiodite-catalyzed oxidative α-C−N coupling of ketones with the corresponding imides and azoles, respectively. The use of inorganic base additives such as cesium carbonate in the presence of 18-crown-6 as a phase transfer catalyst was crucial to induce high reactivity. Control experiments revealed that the basic additives might not only facilitate high-turnover hypoiodite catalysis, but also be involved in the activation of coupling partners.

DOI： 10.1002/adsc.202300716

その他リンク： https://advanced.onlinelibrary.wiley.com/doi/10.1002/adsc.202300716

1,3-Migrative Ring Expansion of Spiroindolenines to Azepino[3,4-b]indoles 査読有り

Tanaka, H; Yasui, T; Uyanik, M; Ishihara, K

ORGANIC LETTERS 25 巻 ( 14 ) 頁： 2377 - 2381 2023年4月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Organic Letters

We serendipitously found an unprecedented 5-to-7-membered ring expansion of 2-alkylspiroindolenines to azepinoindoles mediated by n-tetrabutylammonium fluoride. The starting materials can be easily prepared by the hypoiodite-catalyzed oxidative dearomative spirocyclization of indole derivatives. Mildly basic conditions and electron-deficient protecting groups for the amines were found to be crucial to promoting chemoselective reactions. Moreover, the ring expansion of aniline-derived spiroindolenines proceeds smoothly under much milder conditions using only a catalytic amount of cesium carbonate.

DOI： 10.1021/acs.orglett.3c00207

その他リンク： https://pubs.acs.org/doi/full/10.1021/acs.orglett.3c00207

Catalyst-Substrate Helical Character Matching Determines the Enantioselectivity in the Ishihara-Type Iodoarenes Catalyzed Asymmetric Kita-Dearomative Spirolactonization 査読有り国際共著

Zheng H., Cai L., Pan M., Uyanik M., Ishihara K., Xue X.S.

Journal of the American Chemical Society 145 巻 ( 13 ) 頁： 7301 - 7312 2023年4月

記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of the American Chemical Society

Catalyst design has traditionally focused on rigid structural elements to prevent conformational flexibility. Ishihara’s elegant design of conformationally flexible C2-symmetric iodoarenes, a new class of privileged organocatalysts, for the catalytic asymmetric dearomatization (CADA) of naphthols is a notable exception. Despite the widespread use of the Ishihara catalysts for CADAs, the reaction mechanism remains the subject of debate, and the mode of asymmetric induction has not been well established. Here, we report an in-depth computational investigation of three possible mechanisms in the literature. Our results, however, reveal that this reaction is best rationalized by a fourth mechanism called “proton-transfer-coupled-dearomatization (PTCD)”, which is predicted to be strongly favored over other competing pathways. The PTCD mechanism is consistent with a control experiment and further validated by applying it to rationalize the enantioselectivities. Oxidation of the flexible I(I) catalyst to catalytic active I(III) species induces a defined C2-symmetric helical chiral environment with a delicate balance between flexibility and rigidity. A match/mismatch effect between the active catalyst and the substrate’s helical shape in the dearomatization transition states was observed. The helical shape match allows the active catalyst to adapt its conformation to maximize attractive noncovalent interactions, including I(III)···O halogen bond, N-H···O hydrogen bond, and π···π stacking, to stabilize the favored transition state. A stereochemical model capable of rationalizing the effect of catalyst structural variation on the enantioselectivities is developed. The present study enriches our understanding of how flexible catalysts achieve high stereoinduction and may serve as an inspiration for the future exploration of conformational flexibility for new catalyst designs.

DOI： 10.1021/jacs.2c13295

キラルアンモニウム次亜ヨウ素酸塩触媒を用いるエナンチオ選択的酸化的脱芳香族化反応招待有り

ウヤヌクムハメット, 石原一彰

月間ファインケミカル 51 巻 ( 8 ) 頁： 31 - 39 2022年8月

担当区分：筆頭著者,　責任著者記述言語：日本語掲載種別：研究論文（学術雑誌）

過酸化水素あるいはアルコール過酸化物の存在下、キラルヨウ化第四級アンモニウムからin situで調製される次亜ヨウ素酸塩を触媒活性種に用いるエナンチオ選択的酸化的環化反応を開発した。本酸化システムの詳細な触媒機構を解明することで、高活性な不斉有機酸化触媒システムの構築に成功し、多くの生物活性物質に含まれる2,3-ジヒドロベンゾフラン、クロマン、テトラヒドロフラン、及びスピロラクトン骨格の新規不斉合成を達成した。

Hypoiodite-Catalyzed Oxidative Umpolung of Indoles forEnantioselective Dearomatization 査読有り Open Access

Tanaka, H; Ukegawa, N; Uyanik, M; Ishihara, K

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 144 巻 ( 13 ) 頁： 5756 - 5761 2022年4月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of the American Chemical Society

Here we report the oxidative umpolung of 2,3-disubstituted indoles toward enantioselective dearomative aza-spirocyclization to give the corresponding spiroindolenines using chiral quaternary ammonium hypoiodite catalysis. Mechanistic studies revealed the umpolung reactivity of C3 of indoles by iodination of the indole nitrogen atom. Moreover, the introduction of pyrazole as an electron-withdrawing auxiliary group at C2 suppressed a competitive dissociative racemic pathway, and enantioselective spirocyclization proceeded to give not only spiropyrrolidines but also four-membered spiroazetidines that are otherwise difficult to access.

DOI： 10.1021/jacs.2c01852

その他リンク： https://pubs.acs.org/doi/10.1021/jacs.2c01852

Hypoiodite-catalysed oxidative homocoupling of arenols and tandem oxidation/cross-coupling of hydroquinones with arenes 査読有り

Muhammet Uyanik, Dai Nagata, Kazuaki Ishihara

Chemical Communications 57 巻 ( 88 ) 頁： 11625 - 11628 2021年10月

Oxidative Ritter-type Chloroamidation of Alkenes Using NaCl and Oxone 招待有り査読有り

Takehiro Kato, Yuya Okada, Yuto Fujii, Muhammet Uyanik, Kazuaki Ishihara

Asian Journal of Organic Chemistry 10 巻 ( 11 ) 頁： 2907 - 2910 2021年9月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

A practical and environmentally benign method for the oxidative Ritter-type chloroamidation of alkenes was developed using sodium chloride and oxone as a chlorinating source and an oxidant, respectively. The reaction proceeded smoothly under non-aqueous conditions without the use of any catalyst. Excellent chemoselectivity (i. e., chloroamidation versus dichlorination) could be achieved for electron-deficient styrenes. In addition, this protocol could be easily applied to 7-gram-scale synthesis.

DOI： 10.1002/ajoc.202100575

Chiral Organoiodine-catalyzed Enantioselective Oxidative Dearomatization of Phenols 招待有り査読有り Open Access

Uyanik, M; Ishizaki, S; Ishihara, K

ORGANIC SYNTHESES 98 巻頁： 28 - + 2021年

Synthesis of Chiral Organoiodine Catalyst for Enantioselective Oxidative Dearomatization Reactions: N,N′-(2S,2′S)-(2-Iodo-1,3-phenylene)bis(oxy)bis(propane-2,1-diyl)bis(2,4,6-trimethylbenzamide) 招待有り査読有り Open Access

Uyanik, M; Ishizaki, S; Ishihara, K

ORGANIC SYNTHESES 98 巻頁： 1 - + 2021年

高活性次亜ヨウ素酸塩/過酸化水素触媒システムを用いるカルボニルの酸化的α-アジド化反応

23 巻頁： 10 - 13 2020年12月

I+/TBHP Catalysis For Tandem Oxidative Cyclization To Indolo[2,3-b]quinolines 招待有り査読有り

Muhammet Uyanik, Hiroki Tanaka, Kazuaki Ishihara

Asian Journal of Organic Chemistry 10 巻 ( 1 ) 頁： 164 - 169 2020年11月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

A chemoselective I+/TBHP catalysis was developed for tandem oxidative cyclization/aromatization of indole derivatives under nearly neutral conditions to give the corresponding indolo[2,3-b]quinoline sulfonate salts, which could be easily isolated via only simple filtration of the crude reaction mixture. Interestingly both ionic and radical active species would be generated in situ for the corresponding oxidative transformations to proceed in a chemoselective manner.

DOI： 10.1002/ajoc.202000570

Hypoiodite-Catalyzed Chemoselective Tandem Oxidation of Homotryptamines to Peroxy- and Epoxytetrahydropyridoindolenines 査読有り

Muhammet Uyanik, Hiroki Tanaka, Kazuaki Ishihara

Organic Letters 22 巻 ( 20 ) 頁： 8049 - 8054 2020年9月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

We developed the hypoiodite-catalyzed tandem dearomative peroxycyclization of homotryptamine derivatives to peroxytetrahydropyridoindolenines under mild conditions. During the course of a mechanistic study, we found that a tandem oxidative cyclization/epoxidation as an unexpected reaction proceeded in the presence of TEMPO as an additive. Intramolecular oxidative aminocyclization of homotryptamines at the C-2 position would give tetrahydropyridoindole, a common intermediate for both reactions. Control experiments suggested that while oxidative coupling with TBHP at the C-3 position might afford peroxyindolenines, a preferential electrophilic addition of TEMPO+, which might be generated in situ by the hypoiodite-catalyzed oxidation of TEMPO, at C-3 position followed by elimination and epoxidation might give epoxyindolenines. This serendipitous finding prompted us to develop a chemoselective divergent synthesis of peroxy- and epoxyindolenines by simple modification of the reaction conditions.

DOI： 10.1021/acs.orglett.0c03001

Chemo‐ and Enantioselective Oxidative α-Azidation of Carbonyl Compounds 査読有り

Muhammet Uyanik, Naoto Sahara, Mayuko Tsukahara, Yuhei Hattori, Kazuaki Ishihara

Angewandte Chemie International Edition 59 巻 ( 39 ) 頁： 17110 - 17117 2020年6月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

We report high-performance I+/H2O2 catalysis for the oxidative or decarboxylative oxidative α-azidation of carbonyl compounds by using sodium azide under biphasic neutral phase-transfer conditions. To induce higher reactivity especially for the α-azidation of 1,3-dicarbonyl compounds, we designed a structurally compact isoindoline-derived quaternary ammonium iodide catalyst bearing electron-withdrawing groups. The nonproductive decomposition pathways of I+/H2O2 catalysis could be suppressed by the use of a catalytic amount of a radical-trapping agent. This oxidative coupling tolerates a variety of functional groups and could be readily applied to the late-stage α-azidation of structurally diverse complex molecules. Moreover, we achieved the enantioselective α-azidation of 1,3-dicarbonyl compounds as the first successful example of enantioselective intermolecular oxidative coupling with a chiral hypoiodite catalyst.

DOI： 10.1002/anie.202007552

Chemoselective oxidative generation of ortho-quinone methides and tandem transformations 査読有り

Muhammet Uyanik, Kohei Nishioka, Ryutaro Kondo, Kazuaki Ishihara

Nature Chemistry 12 巻 ( 4 ) 頁： 353 - 362 2020年3月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

ortho-Quinone methides are useful transient synthetic intermediates in organic synthesis. These species are most often generated in situ by the acid- or base-mediated transformation of phenols that have been pre-functionalized at a benzylic position, or by biomimetic oxidation of the corresponding ortho-alkylphenols with metal oxidants or transition-metal complexes. Here we describe a method for the transition-metal-free oxidative generation of o-QMs from ortho-alkylarenols, using hypoiodite catalysis under nearly neutral conditions, which can then be applied in one-pot tandem reactions. This method for the chemoselective oxidative generation of ortho-quinone methides may prove superior to previous methods with respect to environmental issues and scope, and can be applied to various tandem reactions such as inter- or intramolecular [4 + 2] cycloaddition, oxa-6π-electrocyclization, conjugate addition and spiroepoxidation.

DOI： 10.1038/s41557-020-0433-4

Chemoselective Oxidative Spiroetherification and Spiroamination of Arenols Using I+/Oxone Catalysis 査読有り

Muhammet Uyanik, Naoto Sahara, Outa Katade, Kazuaki Ishihara

Organic Letters 22 巻 ( 2 ) 頁： 560 - 564 2019年12月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

We developed a chemoselective oxidative dearomative spiroetherification and spiroamination of arenols using I+/oxone catalysis. The intramolecular dearomative C–O and C–N couplings proceeded much more efficiently under slightly acidic conditions to give the corresponding spiro adducts in higher yields compared with previous methods using transition metal or hypervalent iodine catalysts. Control experiments suggested that both hypoiodous acid and iodine might be active species for these reactions.

DOI： 10.1021/acs.orglett.9b04324

Designer C2-symmetric Chiral Diamide-type Organoiodine Catalysts 招待有り

Muhammet Uyanik, Kazuaki Ishihara

TCI Mail 2019 巻 ( 182 ) 頁： 2 - 16 2019年12月

担当区分：筆頭著者,　責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

As the global issues of environment, energy, and natural resource scarcity increase, the development
of environmentally friendly and efficient catalytic methodologies of organic synthesis is strongly demanded for the sustainable advancement of material civilization. For this purpose, the use of toxic heavy metals and precious transition metals as reactants and/or catalysts should be avoided as much as possible in the synthesis of medicinal and pharmaceutical products. Over the past decades, iodine compounds have been the focus of great attention due to their mild and chemoselective oxidizing properties and their environmentally benign characteristics in contrast to
toxic metal oxidants. Furthermore, the development of chiral hypervalent iodine-catalyzed enantioselective oxidative transformation is one of the most challenging areas in asymmetric organocatalysis. Here, we demonstrate the rational
design of conformationally flexible chiral diamide-type C2-symmetric organoiodine catalysis based on secondary
nonbonding interactions for the enantioselective oxidative dearomatization of arenols. Several research groups
have also reported highly enantioselective oxidative transformations using these conformationally flexible chiral
organoiodine(III) catalysts or reagents. These examples highlight the substantial scope of conformationally flexible designer organoiodine(III) catalysis.

デザイナーC2-対称ジアミド型キラルヨードアレーン触媒招待有り

ウヤヌクムハメット, 石原一彰

TCIメール 2019 巻 ( 182 ) 頁： 2 - 16 2019年12月

担当区分：責任著者記述言語：日本語掲載種別：研究論文（学術雑誌）

環境・エネルギー・資源問題が深刻化するなか，物質文明社会の持続的発展のためには，環境低負荷型触媒的精密有機合成法の開拓が有機合成化学の最重要課題の一つであり，遷移金属等のレアメタルや重金属等の毒性の強い金属資源を反応剤や触媒に用いる従来型の有機合成化学からの脱却が求められている。これに関連し近年，有毒な重金属酸化物の代替物質として超原子価ヨウ素化合物が注目されている。しかし，超原子価ヨウ素の化学は1世紀以上の長い歴史をもつにもかかわらず，不斉酸化反応の成功例はほとんどなく，不斉有機触媒の最も挑戦的な課題の一つとされていた。我々は，それまでの触媒設計概念とは全く異なる配座柔軟性に富むキラルヨードアレーンを分子設計した。本設計は，触媒活性中心（I(III)）と側鎖末端の間に適切な非共有結合性二次的相互作用を導入することで有効な不斉場を構築することを特徴とし，酵素反応に見られる誘導適合のような不斉誘導が可能となる。これらの柔軟かつ機能的な触媒は，様々な酸化的変換反応において世界中で利用されるようになってきている。本総説では我々のC 2対称ジアミド型触媒設計とその応用例について紹介する。

High-Performance Ammonium Hypoiodite/Oxone Catalysis for Enantioselective Oxidative Dearomatization of Arenols 査読有り

Muhammet Uyanik, Takehiro Kato, Naoto Sahara, Outa Katade, Kazuaki Ishihara

ACS Catalysis 9 巻 ( 12 ) 頁： 11619 - 11626 2019年11月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

A high-performance enantioselective quaternary ammonium hypoiodite catalysis was developed for the dearomatization of arenols using oxone as an environmentally benign oxidant. The oxidation of not only 1- and 2-naphthols but also phenols, which were hardly reactive using the previous hypoiodite catalysis, readily proceeded under mild conditions, and only inorganic wastes were generated from the oxidant used. Control experiments and Raman analysis revealed the in situ generation of I+ such as hypoiodous acid as an unstable active species and molecular iodine (I2) as a stable dormant species. Most of the advantages of the present I+/oxone catalysis, compared to previous I+/(H2O2 or ROOH) systems, may result from generation of the stable dormant state and the higher reactivity of catalysts under acidic conditions.

DOI： 10.1021/acscatal.9b04322

Ammonium Hypoiodite-Catalyzed Oxidative Dearomatizative Azidation of Arenols 査読有り

Muhammet Uyanik, Kohei Nishioka, Kazuaki Ishihara

Chemistry Letters 48 巻 ( 4 ) 頁： 353 - 356 2019年1月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

The first transition metal-free catalytic oxidative dearomatizative azidation of arenols has been developed using hypoiodite catalysis with aqueous hydrogen peroxide and trimethylsilyl azide as an oxidant and azide source, respectively, under mild conditions. The corresponding quaternary azides can be obtained in high to excellent yields.

DOI： 10.1246/cl.181036

Front Cover: Regioselective Oxidative Chlorination of Arenols Using NaCl and Oxone (Eur. J. Org. Chem. 1/2019) 査読有り

Muhammet Uyanik, Naoto Sahara, Kazuaki Ishihara

European Journal of Organic Chemistry 2019 巻 ( 1 ) 頁： 1 - 1 2019年1月

Regioselective Oxidative Chlorination of Arenols Using NaCl and Oxone 招待有り査読有り

Muhammet Uyanik, Naoto Sahara, Kazuaki Ishihara

European Journal of Organic Chemistry 2019 巻 ( 1 ) 頁： 27 - 31 2018年10月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

We developed a practical and environmentally benign method for the chlorinative dearomatization of arenols using transient electrophilic chlorinating species generated in situ from inexpensive sodium chloride and Oxone as a Cl source and oxidant, respectively, under mild conditions. Moreover, the regioselective chlorination or chlorinative dearomatization of 1-naphthols was also achieved by changing the reaction conditions.

DOI： 10.1002/ejoc.201801063

Asymmetric Total Synthesis of (-)-Maldoxin, a Common Biosynthetic Ancestor of the Chloropupukeananin Family 査読有り

Takahiro Suzuki, Soichiro Watanabe, Muhammet Uyanik, Kazuaki Ishihara, Susumu Kobayashi, Keiji Tanino

Organic Letters 20 巻 ( 20 ) 頁： 3919 - 3922 2018年6月

記述言語：英語掲載種別：研究論文（学術雑誌）

The total synthesis of pestheic acid based on an intramolecular SNAr reaction without a nitro group and the asymmetric synthesis of (-)-maldoxin by a catalytic enantioselective oxidative dearomatization of pestheic acid are described. The reactivity of (-)-maldoxin as a diene in the Diels-Alder reaction is also investigated.

DOI： 10.1021/acs.orglett.8b01502

Chiral Hypervalent Organoiodine-Catalyzed Enantioselective Oxidative Spirolactonization of Naphthol Derivatives 査読有り

Muhammet Uyanik, Takeshi Yasui, Kazuaki Ishihara

The Journal of Organic Chemistry 82 巻 ( 22 ) 頁： 11946 - 11953 2017年9月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

Highly enantioselective oxidative dearomatization of 2-naphthol derivatives was achieved for the first time by using conformationally flexible organoiodine catalysts derived from 2-aminoalcohol as a chiral source. Moreover, with the use of these catalysts, excellent enantioselectivities were also achieved for 1-naphthol derivatives, which had previously been obtained with only lower enantioselectivities. Furthermore, the product obtained from the present reaction could be transformed to a highly functionalized spirolactone in high yield and with excellent stereoselectivity.

DOI： 10.1021/acs.joc.7b01941

4,5-Dimethyl-2-Iodoxybenzenesulfonic Acid Catalyzed Site-Selective Oxidation of 2-Substituted Phenols to 1,2-Quinols 査読有り

Muhammet Uyanik, Tatsuya Mutsuga, Kazuaki Ishihara

Angewandte Chemie International Edition 56 巻 ( 14 ) 頁： 3956 - 3960 2017年2月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

A site-selective hydroxylative dearomatization of 2-substituted phenols to either 1,2-benzoquinols or their cyclodimers, catalyzed by 4,5-dimethyl-2-iodoxybenzenesulfonic acid with Oxone, has been developed. Furthermore, both the reaction rate and site selectivity could be further improved by the introduction of a trialkylsilylmethyl substituent at the 2-position of phenols. The corresponding 1,2-quinols could be transformed into various useful structural motifs by [4+2] cycloaddition cascade reactions.

DOI： 10.1002/anie.201612463

Ammonium Hypoiodite-Catalyzed Peroxidative Dearomatization of Phenols 招待有り査読有り

Muhammet Uyanik, Kohei Nishioka, Kazuaki Ishihara

Heterocycles 95 巻 ( 2 ) 頁： 1132 - 1147 2017年1月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

Here, we report the first transition metal-free peroxidative dearomatization of phenols using hypoiodite catalysis with TBHP. Hypoiodite salts are generated in situ from the corresponding quaternary ammonium iodides in the presence of TBHP, and the oxidative coupling reaction proceeds efficiently under mild conditions. The dearomatized products are versatile synthetic intermediates for further synthetic transformations to various complex structures including heterocycles. As a demonstration, the further oxidation of the unsaturated peroxide with TBHP afforded the corresponding peroxy epoxide in good yield.

DOI： 10.3987/COM-16-S(S)84

Enantioselective Synthesis of Masked Benzoquinones Using Designer Chiral Hypervalent Organoiodine(III) Catalysis 査読有り

Muhammet Uyanik, Niiha Sasakura, Masahiro Mizuno, Kazuaki Ishihara

ACS Catalysis 7 巻 ( 1 ) 頁： 872 - 876 2016年12月

キラル第四級アンモニウム次亜ヨウ素酸塩触媒招待有り

ウヤヌクムハメット, 石原一彰

月間ファインケミカル 45 巻 ( 12 ) 頁： 16 - 24 2016年12月

担当区分：筆頭著者,　責任著者記述言語：日本語掲載種別：研究論文（学術雑誌）

Chiral Ammonium Hypoiodite Salt-Catalyzed Enantioselective Oxidative Cycloetherification to 2-Acyl Tetrahydrofurans 査読有り

Muhammet Uyanik, Hiroki Hayashi, Hirokazu Iwata, Kazuaki Ishihara

Chemistry Letters 45 巻 ( 3 ) 頁： 353 - 355 2016年1月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

2-Acyl tetrahydrofuran is a fundamental structure in natural products and pharmaceuticals. We achieved a chiral quaternary ammonium hypoiodite salt-catalyzed enantioselective oxidative cycloetherification of δ-hydroxyketone derivatives. The corresponding 2-acyl tetrahydrofurans were obtained in high chemical yield with high enantioselectivity.

DOI： 10.1246/cl.160004

Practical Oxidative Dearomatization of Phenols with Sodium Hypochlorite Pentahydrate 査読有り

Muhammet Uyanik, Niiha Sasakura, Mitsuyoshi Kuwahata, Yasukazu Ejima, Kazuaki Ishihara

Chemistry Letters 44 巻 ( 3 ) 頁： 381 - 383 2015年2月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

A highly efficient and practical oxidative dearomatization of phenols using sodium hypochlorite pentahydrate as an inexpensive, strong oxidant is reported for the first time. The oxidation reactions proceeded very rapidly in the presence of water to give the desired products in excellent yields, and sodium chloride and water were the only by-products derived from the oxidant.

DOI： 10.1246/cl.141130

High-Performance Hypoiodite/Hydrogen Peroxide Catalytic System for the Oxylactonization of Aliphatic γ-Oxocarboxylic Acids 査読有り

Muhammet Uyanik, Daisuke Suzuki, Mizu Watanabe, Hiroyasu Tanaka, Kikuo Furukawa, Kazuaki Ishihara

Chemistry Letters 44 巻 ( 3 ) 頁： 387 - 389 2015年2月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

Highly efficient hypoiodite-catalyzed oxylactonization of aliphatic γ-oxocarboxylic acids to the corresponding γ-acyl-γ-butyrolactones was developed. Highly dilute reaction conditions and slow addition of the oxidant are each highly effective for promoting the high-performance hypoiodite/hydrogen peroxide catalytic oxidation system.

DOI： 10.1246/cl.141110

Chiral Ammonium Hypoiodite-catalyzed Enantioselective Oxidative Dearomatization of 1-Naphthols Using Hydrogen Peroxide 査読有り

Muhammet Uyanik, Niiha Sasakura, Erina Kaneko, Kento Ohori, Kazuaki Ishihara

Chemistry Letters 44 巻 ( 2 ) 頁： 179 - 181 2015年2月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

A highly enantioselective oxidative dearomatization of 1-naphthol derivatives (Kita spirolactonization) catalyzed by chiral hypoiodite species prepared in situ from chiral quaternary ammonium iodide in the presence of hydrogen peroxide is reported.

DOI： 10.1246/cl.141012

High-turnover hypoiodite catalysis for asymmetric synthesis of tocopherols 査読有り

Muhammet Uyanik, Hiroki Hayashi, Kazuaki Ishihara

Science 345 巻 ( 6194 ) 頁： 291 - 294 2014年7月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

The diverse biological activities of tocopherols and their analogs have inspired considerable interest in the development of routes for their efficient asymmetric synthesis. Here, we report that chiral ammonium hypoiodite salts catalyze highly chemo- and enantioselective oxidative cyclization of γ-(2-hydroxyphenyl)ketones to 2-acyl chromans bearing a quaternary stereocenter, which serve as productive synthetic intermediates for tocopherols. Raman spectroscopic analysis of a solution of tetrabutylammonium iodide and tert-butyl hydroperoxide revealed the in situ generation of the hypoiodite salt as an unstable catalytic active species and triiodide salt as a stable inert species. A high-performance catalytic oxidation system (turnover number of ~200) has been achieved through reversible equilibration between hypoiodite and triiodide in the presence of potassium carbonate base. We anticipate that these findings will open further prospects for the development of high-turnover redox organocatalysis.

DOI： 10.1126/science.1254976

2-ヨードベンゼンスルホン酸(pre-IBS)とOxoneを用いる選択的酸化反応招待有り

ウヤヌクムハメット, 六鹿達矢, 石原一彰

和光純薬時報 81 巻 ( 4 ) 頁： 5 - 9 2013年10月

担当区分：筆頭著者記述言語：日本語掲載種別：研究論文（研究会，シンポジウム資料等）

著者らはIBXよりも遥かに活性が高く、選択性の優れたIBS触媒系を開発することができた。1–5 mol%のpre-IBSを用いて、第1級又は第2級アルコールを対応するアルデヒドやカルボン酸、またはケトンへ効率よく酸化できた。また、環状アルコールから触媒的カスケード型酸化反応によって環状エノンやラクトンを高収率で合成できた。さらに、本触媒的酸化システムをtert-アリルアルコールの転位／酸化反応及びフェノールのオルト選択的酸化反応に拡張することにも成功した。本IBS/Oxoneの触媒的酸化システムは、国内外の他の研究グループも加わり、さらに発展しつつある。今後も、触媒的IBS酸化はさらなる応用的発展が期待され、環境低負荷型酸化システムとして定着するであろう。

Hydrogen Bonding and Alcohol Effects in Asymmetric Hypervalent Iodine Catalysis: Enantioselective Oxidative Dearomatization of Phenols 査読有り

Muhammet Uyanik, Takeshi Yasui, Kazuaki Ishihara

Angewandte Chemie International Edition 52 巻 ( 35 ) 頁： 9215 - 9218 2013年6月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

A conformationally flexible C2-symmetric organoiodine(III) catalyst for the highly enantioselective catalytic oxidative dearomatization of phenols has been developed. Catalysis is controlled by intramolecular hydrogen-bonding interactions and additional achiral alcohols.

DOI： 10.1002/anie.201303559

Baeyer-Villiger Oxidation Using Hydrogen Peroxide 招待有り査読有り

Muhammet Uyanik, Kazuaki Ishihara

ACS Catalysis 3 巻 ( 5 ) 頁： 513 - 520 2013年2月

担当区分：筆頭著者記述言語：英語

The Baeyer-Villiger (BV) oxidation of carbonyl compounds to the corresponding esters or lactones is one of the most important transformations. We recently introduced a highly efficient and selective LiB(C6F5)4- or Ca[B(C6F5)4]2-catalyzed BV oxidation of ketones with aqueous hydrogen peroxide to give the corresponding lactones in high yield. In this perspective article, we focus on our discovery and the development of BV oxidation reactions and cascade oxidative transformations through representative metal catalysts and organocatalysts.

DOI： 10.1021/cs300821u

Conformationally-Flexible Chiral Hypervalent Organoiodine Catalysts for Enantioselective Oxidative Transformations 招待有り査読有り Open Access

Uyanik, M; Ishihara, K

JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN 70 巻 ( 11 ) 頁： 1116 - 1122 2012年11月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry

The development of chiral hypervalent iodine-catalyzed oxidative transformations is one of the most challenging areas in asymmetric organocatalysis. Although several elegant chiral hypervalent iodine(III and V) reagents or catalysts had been developed for various asymmetric oxidation reactions, the enantioselectivities had been moderate before our paper was published in 2010. We have had a great interest in the development of organocatalysis based on hypervalent chemistry since 2007. In this account, we describe our design concept of conformationally-flexible chiral hypervalent organoiodine(III), and the results obtained for catalytic use of our chiral iodines(III) for enantioselective Kita oxidative spirolactonization. Additionally, other chiral hypervalent iodine-mediated asymmetric oxidation reactions reported after our publications are also highlighted briefly.

DOI： 10.5059/yukigoseikyokaishi.70.1116

Baeyer-Villiger Oxidation and Oxidative Cascade Reactions with Aqueous Hydrogen Peroxide Catalyzed by Lipophilic Li[B(C₆F₅)₄] and Ca[B(C₆F₅)₄]₂ 査読有り

Muhammet Uyanik, Daisuke Nakashima, Kazuaki Ishihara

Angewandte Chemie International Edition 51 巻 ( 36 ) 頁： 9093 - 9096 2012年8月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

We have developed highly efficient and selective Li[B(C6F5)4] or Ca[B(C6F5)4]2 catalyzed Baeyer-Villiger (BV) oxidations of various cycloalkanones with 30-wt% aqueous hydrogen peroxide to give the corresponding lactones in high yield. Additionally, we have found that the reaction rate is accelerated with the use of oxalic acid as a co-catalyst. Moreover, beta-silyl cyclohexanones can be oxidized to either the corresponding unsaturated carboxylic acids or hydroxylactones in high yields through BV oxidation/b-elimination reaction sequences and subsequent epoxidation/cyclization reaction sequences, by controlling the amounts of H2O2 and oxalic acid. These reactions proceed under mild conditions and tolerate various functional groups.

DOI： 10.1002/anie.201204286

デザイン型ヨウ素触媒を用いる環境調和型選択的酸化反応査読有り

ウヤヌクムハメット

化学と工業 65 巻 ( 8 ) 頁： 625 - 626 2012年8月

担当区分：筆頭著者記述言語：日本語掲載種別：研究論文（大学，研究機関等紀要）

ヨウ素は容易に酸化されてその原子価を拡張し、超原子価状態となるため、遷移金属のような酸化・還元性を示す。我々は、ヨウ素のこの超原子価性に着目し、従来の毒性の強い重金属酸化剤や遷移金属触媒に代わる非金属系超原子価ヨウ素触媒による幾つかの高選択的環境調和型酸化反応の開発に成功した。

IBS-Catalyzed Regioselective Oxidation of Phenols to 1,2-Quinones with Oxone 招待有り査読有り

Muhammet Uyanik, Tatsuya Mutsuga, Kazuaki Ishihara

Molecules 17 巻 ( 7 ) 頁： 8604 - 8616 2012年7月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

We have developed the first example of hypervalent iodine(V)-catalyzed regioselective oxidation of phenols to ortho-quinones. Various phenols could be oxidized to the corresponding ortho-quinones in good to excellent yields using catalytic amounts of sodium salts of 2-iodobenzenesulfonic acids (pre-IBSes) and stoichiometric amounts of Oxone as a co-oxidant under mild conditions. The reaction rate of IBS-catalyzed oxidation under nonaqueous conditions was further accelerated in the presence of an inorganic base such as potassium carbonate (K2CO3), a phase transfer catalyst such as tetrabutylammonium hydrogen sulfate (n-Bu4NHSO4), and a dehydrating agent such as anhydrous sodium sulfate (Na2SO4).

DOI： 10.3390/molecules17078604

Catalysis with In Situ-Generated (Hypo)iodite Ions for Oxidative Coupling Reactions 招待有り査読有り

Muhammet Uyanik, Kazuaki Ishihara

ChemCatChem 4 巻 ( 2 ) 頁： 177 - 185 2011年12月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

This Concept highlights the discovery and development of oxidative coupling reactions catalyzed by the hypoiodite (IO) or iodite (IO2) ion, which are generated in situ from iodide (I-) ion with hydrogen peroxide or tert-butyl hydroperoxide as an environmentally benign oxidant. The most important features of these catalytic systems are 1) metal-free oxidation, 2) milder reaction conditions, 3) high chemoselectivity (they tolerate a wide range of various functional groups), 4) operational simplicity, and 5) water or tert-butyl alcohol as the only byproduct derived from the co-oxidant used.

DOI： 10.1002/cctc.201100352

2-Iodoxy-5-Methylbenzenesulfonic Acid-Catalyzed Selective Oxidation of 4-Bromobenzyl Alcohol to 4-Bromobenzaldehyde or 4-Bromobenzoic Acid with Oxone 招待有り査読有り

Muhammet Uyanik, Kazuaki Ishihara, Margaret Faul, Richard Crockett

Organic Syntheses 89 巻頁： 105 - 114 2011年9月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

We have reported that 2-iodoxybenzenesulfonic acids (IBSs) which are in situ prepared from Oxone and 2-iodobenzenesulfonic acids show efficient catalytic activity on the alcohol oxidation under mild conditions. Here, we succeeded in scale up of the IBS-catalyzed alcohol oxidations.

DOI： 10.15227/orgsyn.089.0105

In Situ Generated (Hypo)Iodite Catalysts for the Direct α-Oxyacylation of Carbonyl Compounds with Carboxylic Acids 査読有り

Muhammet Uyanik, Daisuke Suzuki, Takeshi Yasui, Kazuaki Ishihara

Angewandte Chemie International Edition 50 巻 ( 23 ) 頁： 5331 - 5334 2011年5月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

The intra- and intermolecular title reaction is catalyzed by an in situ generated ammonium (hypo)iodite species. Either H2O2 or tert-butyl hydroperoxide (TBHP) can be used as an environmentally benign oxidant and a wide range of substrates react to give the corresponding alpha-acyloxycarbonyl compounds in good to excellent yields.

DOI： 10.1002/anie.201101522

非共有結合相互作用を利用したキラル超原子価ヨウ素触媒の開発：北スピロラクトン化反応への応用招待有り

ウヤヌクムハメット, 安井猛, 石原一彰

和光純薬時報 79 巻 ( 2 ) 頁： 2-5 2011年4月

担当区分：筆頭著者記述言語：日本語

我々は2 , 6 -ジヒドロキシヨードベンゼンを基本骨格とし、乳酸をキラル源に柔軟な立体配座とC 2 対称性を保持したキラルヨードアレンの合理的設計を考案した。この有効性を実証するため、m -CPBA存在下、触媒量のヨードアレンから超原子価ヨウ素（III）触媒をin situ で調製し、1-ヒドロキシナフチルカルボン酸の北スピロラクトン化反応に試したところ、高い不斉収率で目的のスピロラクトンを得ることに成功した。現在、触媒前駆体は和光純薬から市販されている。本触媒技術で合成出来る光学活性スピロラクトンはさらに様々な合成変換が可能であることから、その応用範囲は広く、医薬品の製造技術としても期待される。これらの結果は、キラル超原子価ヨウ素化合物の設計、及びエナンチオ選択的酸化的カップリング反応の発展に大きく寄与するものと思われる。

In Situ-Generated Chiral Quaternary Ammonium (Hypo)iodite Catalysis for Enantioselective Oxidative Cyclisations 招待有り査読有り

Muhammet Uyanik, Kazuaki Ishihara

Chimica Oggi-Chemistry Today 29 巻 ( 1 ) 頁： 18 - 21 2011年1月

担当区分：筆頭著者記述言語：英語

Very recently, we developed the first enantioselective oxidative cycloetherification of ketophenols to 2-acyl-2,3-dihydrobenzofuran derivatives catalysed by in situ generated chiral quaternary ammonium (hypo)iodite with hydrogen peroxide or tert-butyl hydroperoxide (TBHP) as an environmentally benign ideal oxidant. The optically active
2-acyl 2,3-dihydrobenzofuran skeleton is a key structure in
several medicinally and biologically active compounds.

In situ-generated chiral quaternary ammonium (hypo)iodite catalysis for enantioselective oxidative cyclisations 招待有り査読有り

Uyanik, M; Ishihara, K

CHIMICA OGGI-CHEMISTRY TODAY 29 巻 ( 1 ) 頁： 18 - 21 2011年1月

2-Iodoxybenzenesulfonic Acid (IBS)-Catalyzed Oxidation of Alcohols 招待有り査読有り

43 巻 ( 3 ) 頁： 83 - 91 2010年12月

金属を使わない不斉酸化的カップリング触媒無機ヨウ素酸塩へのブレークスルー招待有り

石原一彰, UYANIK Muhammet

化学 65 巻 ( 10 ) 頁： 12 - 17 2010年9月

記述言語：日本語掲載種別：研究論文（研究会，シンポジウム資料等）

触媒にキラルヨウ素酸塩を用い、共酸化剤に過酸化水素を用いた不斉分子内酸化的エーテル環化反応を開発した。金属を全く用いず、水のみを副生成物とする、常温、常圧下の理想的な不斉酸化的カップリングの成功である。本研究成果は2010年6月に米国科学誌「サイエンス」に掲載された)。本稿では、その開発の経緯、内容、意義について解説する。

Quaternary Ammonium (Hypo)iodite Catalysis for Enantioselective Oxidative Cycloetherification 査読有り

Muhammet Uyanik, Hiroaki Okamoto, Takeshi Yasui, Kazuaki Ishihara

Science 328 巻 ( 5984 ) 頁： 1376 - 1379 2010年6月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

It is desirable to minimize the use of rare or toxic metals for oxidative reactions in the synthesis of pharmaceutical products. Hypervalent iodine compounds are environmentally benign alternatives, but their catalytic use, particularly for asymmetric transformations, has been quite limited. We report here an enantioselective oxidative cycloetherification of ketophenols to 2-acyl-,3-dihydrobenzofuran derivatives, catalyzed by in situ generated chiral quaternary ammonium (hypo)iodite salts, with hydrogen peroxide as an environmentally benign oxidant. The optically active 2-acyl 2,3-dihydrobenzofuran skeleton is a key structure in several biologically active compounds.

DOI： 10.1126/science.1188217

Chiral Hypervalent Iodine-Catalyzed Enantioselective Oxidative Kita Spirolactonization of 1-Naphthol Derivatives and One-Pot Diastereoselective Oxidation to Epoxyspirolactones 招待有り査読有り

Muhammet Uyanik, Takeshi Yasui, Kazuaki Ishihara

Tetrahedron 66 巻 ( 31 ) 頁： 5841 - 5851 2010年4月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

We demonstrate here the rational design of a conformationally flexible C2-symmetric iodosylarene 8g based on secondary n-sigma* or hydrogen-bonding interactions as a chiral catalyst for the enantioselective Kita oxidative spirolactonization of 1-naphthol derivatives 5. Iodosylarenes 8 were generated in situ from iodoarenes 7 and mCPBA as a co-oxidant. Furthermore, epoxyspirolactone 15 was obtained by the one-pot oxidation of 5 with mCBPA in the presence of 7g. Thus, the enantioselective oxidation of 5 to 6 and the successive enantio- and diastereo-selective oxidation of 5 to 15 proceeded in good yields when we controlled the amount of mCPBA.

DOI： 10.1016/j.tet.2010.04.060

Enantioselective Kita Oxidative Spirolactonization Catalyzed by In Situ Generated Chiral Hypervalent Iodine(III) Species 査読有り

Muhammet Uyanik, Takeshi Yasui, Kazuaki Ishihara

Angewandte Chemie International Edition 49 巻 ( 12 ) 頁： 2175 - 2177 2010年3月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

Conformationally flexible C2-symmetric chiral iodosylarene, which has been rationally designed based on secondary n-σ* or hydrogen-bonding interactions, is a highly effective catalyst for the Kita oxidative spirolactonization. The present catalysis is applicable to a broader range of substrates and provides the highest enantioselectivity (up to 92% ee) among previous chiral hypervalent iodine-catalyzed reactions.

DOI： 10.1002/anie.200907352

Bromine-Catalyzed Aerobic Oxidation of Alcohols 招待有り査読有り

Muhammet Uyanik, Ryota Fukatsu, Kazuaki Ishihara

Chemistry-An Asian Journal 5 巻 ( 3 ) 頁： 456 - 460 2010年2月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

We demonstrated that a simple and environmentally benign catalytic system HBr/NaNO2 is very effective for the selective oxidation of alcohols under balloon pressure of O2. Furthermore, the aerobic oxidation of alcohols was also achieved under balloon pressure of air instead of pure O2 with this HBr/NaNO2/HNO3 catalytic system.

DOI： 10.1002/asia.200900609

2-Iodoxybenzenesulfonic Acid (IBS) Catalyzed Oxidation of Alcohols 招待有り査読有り

Uyanik, M; Ishihara, K

ALDRICHIMICA ACTA 43 巻 ( 3 ) 頁： 83 - 91 2010年

IBS-Catalyzed Oxidative Rearrangement of Tertiary Allylic Alcohols to Enones with Oxone 査読有り

Muhammet Uyanik, Ryota Fukatsu, Kazuaki Ishihara

Organic Letters 11 巻 ( 15 ) 頁： 3470 - 3473 2009年7月

Hypervalent iodine-catalyzed oxylactonization of ketocarboxylic acids to ketolactones 招待有り査読有り

Muhammet Uyanik, Takeshi Yasui, Kazuaki Ishihara

Bioorganic & Medicinal Chemistry Letters 19 巻 ( 14 ) 頁： 3848 - 3851 2009年4月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

The hypervalent iodine-catalyzed oxylactonization of ketocarboxylic acids to ketolactones was achieved in the presence of iodobenzene (10 mol%), p-toluenesulfonic acid monohydrate (20 mol%) and meta-chloroperbenzoic acid as a stoichiometric co-oxidant.

DOI： 10.1016/j.bmcl.2009.03.148

Hypervalent Iodine-Mediated Oxidation of Alcohols 招待有り査読有り

Muhammet Uyanik, Kazuaki Ishihara

Chemical Communications 2009 巻 ( 16 ) 頁： 2086 - 2099 2009年3月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）

Over the past two decades there has been a dramatic increse in the use of hypervalent iodine compounds in synthetic organic chemistry due to their mild and selective oxidizing properties. Hypervalent iodine compounds catalyze various oxidation reactions such as the oxidation of alcohols, alpha-oxidation of ketones, oxidative spirocyclization of phenols, etc. Very recently, we found that 2-iodoxybenzensulfonic acid (IBS), which was generated from 2-iodobenzenesulfonic acid in situ, was an extremely active and mild catalyst for the highly chemoselective oxidation of various alcohols with powdered Oxone to carbonyl compounds such as aldehydes, carboxylic acids, ketones and cycloalkenones under nonaqueous conditions. In this review, we focus on the design of hypervalent iodine catalysts and review the discovery and development of the oxidation of alcohols with the stoichiometric or catalytic use of hypervalent iodine compounds.

DOI： 10.1039/b823399c

2-Iodoxybenzenesulfonic Acid as an Extremely Active Catalyst for the Selective Oxidation of Alcohols to Aldehydes, Ketones, Carboxylic Acids, and Enones with Oxone 査読有り国際誌

Uyanik, M; Akakura, M; Ishihara, K

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 131 巻 ( 1 ) 頁： 251 - 262 2009年1月

担当区分：筆頭著者記述言語：英語掲載種別：研究論文（学術雑誌）出版者・発行元：Journal of the American Chemical Society

Electron-donating group-substituted 2-iodoxybenzoic acids (IBXs) such as 5-Me-IBX (1g), 5-MeO-IBX (1h), and 4,5-Me2-IBX were superior to IBX 1a as catalysts for the oxidation of alcohols with Oxone (a trademark of DuPont) under nonaqueous conditions, although Oxone was almost insoluble in most organic solvents. The catalytic oxidation proceeded more rapidly and cleanly in nitromethane. Furthermore, 2-iodoxybenzenesulfonic acid (IBS, 6a) was much more active than modified IBXs. Thus, we established a highly efficient and selective method for the oxidation of primary and secondary alcohols to carbonyl compounds such as aldehydes, carboxylic acids, and ketones with Oxone in nonaqueous nitromethane, acetonitrile, or ethyl acetate in the presence of 0.05-5mol%of 6a, which was generated in situ from 2-iodobenzenesulfonic acid (7a) or its sodium salt. Cycloalkanones could be further oxidized to α,β- cycloalkenones or lactones by controlling the amounts of Oxone under the same conditions as above. When Oxone was used under nonaqueous conditions, Oxone wastes could be removed by simple filtration. Based on theoretical calculations, we considered that the relatively ionic character of the intramolecular hypervalent iodine-OSO2 bond of IBS might lower the twisting barrier of the alkoxyperiodinane intermediate 16. © 2009 American Chemical Society.

DOI： 10.1021/ja807110n