Jan. 2022, American Chemical Society, Citations for Chemical Breakthrough Awards　　　　　　　　　　　　　　　
Asymmetric Hydrogenation of β-Keto Carboxylic Esters. A Practical Curly Chemical Access to β-Hydroxy Esters in High Enantiomeric Purity, J. Am. Chem. Soc. 1987, 109, 5856-5858.
R. Noyori;T. Ohkuma;M. Kitamura (Nagoya University);H. Takaya (Institute for Molecular Science);N. Sayo;H. Kumabayashi;S. Akutagawa (Takasago International Corporation).

Mar. 2018, Chemical Society of Japan, The 35th Excellent Scholar Award　　　　　　　　　　　　　　　
Development of Asymmetric Reactions Catalyzed by Ruthenium Complexes with Two Kinds of Ligands
OHKUMA Takeshi

Dec. 2014, University of Malaya, Asian Core Program Lectureship Award　　　　　　　　　　　　　　　
OHKUMA Takeshi

Jun. 2007, International Scientist of the Year 2007　　　　　　　　　　　　　　　

Mar. 2007, 第３回日本学術振興会賞　　　　　　　　　　　　　　　
Japan

2007, International Scientist of the Year 2007　　　　　　　　　　　　　　　

2007, JSPS Prize　　　　　　　　　　　　　　　

Jun. 2005, 慶應義塾大学同窓会, 研究教育奨励基金による表彰者　　　　　　　　　　　　　　　
大熊 毅

Feb. 2000, 有機合成化学協会, エヌ・イー ケムキャット研究企画賞　　　　　　　　　　　　　　　
大熊 毅

Feb. 1998, 有機合成化学奨励賞　　　　　　　　　　　　　　　
大熊 毅

Exclusive Papers of the Editorial Board Members and Topical Advisory Panel Members of Catalysts in Section “Catalysis in Organic and Polymer Chemistry”
Kotohiro Nomura, Raffaella Mancuso, Zhengguo Cai, Samuel Dagorne, Moris S. Eisen, Luca Gonsalvi, Martin Kotora, Bun Yeoul Lee, Shaofeng Liu, Luísa Margarida Martins, Takeshi Ohkuma, Armando Pombeiro, Fabio Ragaini, Carl Redshaw, Marc Visseaux, Zongquan Wu, Hiroto Yoshida, Masamichi Ogasawara
Catalysts, 14, 7, 407, MDPI AG, 27 Jun. 2024, [Invited]
English, Scientific journal, Herein, I would like to provide an overview of this Special Issue, published in the Organic and Polymer Chemistry Section of Catalysis, comprising contributions from 18 of the journal’s Editorial Board Members [...]

Asymmetric Cyanation of α-Ketimino Ester Derivatives with Chiral Ru–Li Combined Catalysts
Taiga Yurino, Zhen Wu, Kazuaki Suzuki, Rino Nitta, Yusuke Sakaguchi, Takeshi Ohkuma
Organic Letters, 26, 900, 905, American Chemical Society (ACS), 22 Jan. 2024, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, 13483696

Asymmetric Hydrogenation of α-Alkyl-Substituted β-Keto Esters and Amides through Dynamic Kinetic Resolution
Taiga Yurino, Ryo Nishihara, Toshihisa Yasuda, Shuangli Yang, Noriyuki Utsumi, Takeaki Katayama, Noriyoshi Arai, Takeshi Ohkuma
Organic Letters, 26, 2872, 2876, 05 Jan. 2024, [Peer-reviewed], [Invited], [Last author, Corresponding author]
English, Scientific journal, 13483696

Ru(η1-BH4)(daipena)(diphosphine): Ruthenabicyclic borohydride complexes for asymmetric hydrogenation of ketones and asymmetric formal hydroamination of allylic alcohols under base-free conditions
Tomohiro Ishizaka, Yuji Nakayama, Taichiro Touge, Yamato Yuki, Kazuhiko Matsumura, Taiga Yurino, Takeshi Ohkuma
Tetrahedron, 133705, 133705, Elsevier BV, 14 Oct. 2023, [Peer-reviewed], [Invited], [Last author, Corresponding author]
English, Scientific journal, 13483696

Ag-Catalyzed Cyanomethylation of Amines Using Nitromethane as a C1 Source
Takuya Takashima, Hamdiye Ece, Taiga Yurino, Takeshi Ohkuma
Organic Letters, 25, 25, 6052, 6056, American Chemical Society (ACS), 10 Aug. 2023, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, 13483696

Development of Catalytic Isocyanation via Precise Reactivity Control of Ambident Reagent
Taiga Yurino, Takeshi Ohkuma
Journal of Synthetic Organic Chemistry, Japan, 81, 3, 235, 243, The Society of Synthetic Organic Chemistry, Japan, 01 Mar. 2023, [Peer-reviewed], [Invited], [Last author, Corresponding author]
Japanese, Scientific journal, 13483696

Asymmetric Hydrogenation of α-Amino Esters into Optically Active β-Amino Alcohols through Dynamic Kinetic Resolution Catalyzed by Ruthenabicyclic Complexes
Hiroki. Ishikawa, Taiga Yurino, Ryo Komatsu, Ming-Yuan Gao, Noriyoshi Arai, Takeshi Ohkuma
Organic Letters, 25, 2355, 2360, American Chemical Society (ACS), Mar. 2023, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, 13483696

Potassium Alkoxide as an Efficient Catalyst for Nucleophilic Perfluoroalkylation: Attempt at Anion-Controlled Enantioselective Insertion of a Trifluoromethyl Group
Taiga Yurino, Takeshi Ohkuma, Hiroyuki Yamashita, Yuanrong Shan, Zhen Wu
Synlett, 33, 17, 1739, 1744, Georg Thieme Verlag KG, Oct. 2022, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, Abstract

Potassium alkoxide was found to be a highly active catalyst for the nucleophilic trifluoromethylation of carbonyl compounds. The catalytic system was successfully applied to the reactions of both aldehydes and ketones, affording the corresponding trifluoromethylated products in high yields at low catalyst loadings (0.1–0.01 mol%) in several solvents, such as THF, toluene, and CH2Cl2. In addition, the potassium salt of a Ru(II) complex bearing an (S)-2,2′-bis[bis(3,5-dimethylphenyl)phosphinyl]-1,1′-binaphthalene [ (S)-XylBINAP] ligand and two l-threoninate ligands, prepared in situ, catalyzed the enantioselective trifluoromethylation of aromatic aldehydes, although the ee values were not satisfactory (less than 20%)., 13483696

Aerobic Allylic Amination Catalyzed by Pd(OAc)2/P(OPh)3 System with Low Catalyst Loading
Taiga Yurino, Sunaho Saito, Mizuki Ichihashi, Takeshi Ohkuma
The Journal of Organic Chemistry, 87, 2864, 2872, American Chemical Society (ACS), Jan. 2022, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal, 13483696

Stereoselective construction of cycloheptene-fused indoline frameworks through photosensitised formal [5+2] cycloaddition
Noriyoshi Arai, Takeshi Ohkuma
Tetrahedron Letters, 88, 153588, 153588, Elsevier BV, Jan. 2022, [Peer-reviewed], [Last author, Corresponding author]
English, Scientific journal

Palladium-Catalyzed Nucleophilic Isocyanation for the Synthesis of α-Aryl-α-Isocyanoacetoamide Derivatives
Taiga Yurino, Yuji Tange, Takeshi Ohkuma
Bulletin of the Chemical Society of Japan, 94, 9, 2155, 2161, The Chemical Society of Japan, 15 Sep. 2021, [Peer-reviewed], [Corresponding author]
English, Scientific journal

Asymmetric (Transfer) Hydrogenation of Functionalized Ketones
Noriyoshi Arai, Takeshi Ohkuma
Asymmetric Hydrogenation and Transfer Hydrogenation, 55, 85, Wiley, 26 Apr. 2021

Silyl Cyanopalladate-Catalyzed Friedel–Crafts-Type Cyclization Affording 3-Aryloxindole Derivatives
Hamdiye Ece, Yuji Tange, Taiga Yurino, Takeshi Ohkuma
Synlett, 32, 935, 939, Georg Thieme Verlag KG, 26 Jan. 2021, [Peer-reviewed], [Corresponding author]
English, Scientific journal, 3-Aryloxindole derivatives were synthesized through a Friedel–Crafts-type cyclization. The reaction was catalyzed by a trimethylsilyl tricyanopalladate complex generated in situ from trimethylsilyl cyanide and Pd(OAc)2. Wide varieties of diethyl phosphates derived from N-arylmandelamides were converted almost quantitatively into oxindoles. When N,N-dibenzylamide was used instead of an anilide substrate, a benzo-fused δ-lactam was obtained. An oxindole product was subjected to substitution reactions to afford 3,3-diaryloxindoles with two different aryl groups., 13483696

Photosensitized Intramolecular [2+2] Cycloaddition of 1H-Pyrrolo[2,3-b]pyridines Enabled by the Assistance of Lewis Acids
Noriyoshi Arai, Takeshi Ohkuma
The Journal of Organic Chemistry, 85, 23, 15717, 15725, American Chemical Society (ACS), 04 Dec. 2020, [Peer-reviewed], [Corresponding author]
English, Scientific journal, 13483696

〔巻頭言〕伝えることの大切さと難しさ　　　　　　　　　　　　　　　
大熊毅
有機合成化学協会誌, 78, 8, 759, 759, Aug. 2020, [Invited], [Corresponding author]

Selective Conversion of Benzylic Phosphates into Diarylmethanes Through Al(OTf)3-Catalyzed Friedel-Crafts-Type Benzylation
Taiga Yurino, Asuka Hachiya, Keisuke Suzuki, Takeshi Ohkuma
European Journal of Organic Chemistry, 2020, 15, 2225, 2232, Wiley, 23 Apr. 2020, [Peer-reviewed], [Corresponding author]
English, Scientific journal, 13483696

Friedel−Crafts‐Type Allylation of Phenol Derivatives Catalyzed by In Situ‐Generated Silyl Cyanometallates
Taiga Yurino, Hamdiye Ece, Takeshi Ohkuma
Asian Journal of Organic Chemistry, 9, 4, 557, 560, Wiley, Apr. 2020, [Peer-reviewed], [Invited]
English, Scientific journal, 13483696

Nucleophilic Isocyanation
Taiga Yurino, Takeshi Ohkuma
ACS Omega, 5, 10, 4719, 4724, American Chemical Society (ACS), 17 Mar. 2020, [Peer-reviewed], [Invited], [Corresponding author]
English, Scientific journal, 13483696

Ag2O-catalysed nucleophilic isocyanation: selective formation of less-stable benzylic isonitriles
Taiga Yurino, Yuji Tange, Ryutaro Tani, Takeshi Ohkuma
Organic Chemistry Frontiers, 7, 11, 1308, 1313, Royal Society of Chemistry (RSC), 2020, [Peer-reviewed], [Corresponding author]
English, Scientific journal,

Both primary and secondary benzylic isonitriles were exclusively produced by the Ag₂O-catalysed reaction of benzylic phosphates and trimethylsilyl cyanide without formation of the thermodynamically favoured regioisomers, benzylic nitriles.

, 13483696

Stereoselective Preparation of Methylenecyclobutane-fused Angular Tetracyclic Spiroindolines via Photosensitized Intramolecular [2+2] Cycloaddition with Allene
Noriyoshi Arai, Takeshi Ohkuma
Tetrahedron Letters, 60, 46, 151252, 151255, Elsevier BV, Nov. 2019, [Peer-reviewed]
English, Scientific journal

Isomerization–Asymmetric Hydrogenation Sequence Converting Racemic β-Ylidenecycloalkanols into Stereocontrolled β-Substituted Cycloalkanols Using a Ru Catalytic System with Dual Roles　　　　　　　　　　　　　　　
Noriyoshi Arai, Yuki Okabe, Takeshi Ohkuma
Advanced Synthesis & Catalysis, 361, 24, 5540, 5547, Nov. 2019, [Peer-reviewed]
English, Scientific journal

Asymmetric Hydrogenation of Mines Catalyzed by Ruthenium Complexes　　　　　　　　　　　　　　　
Takeshi Ohkuma
Catalyst, 61, 5, 291, 297, Oct. 2019, [Peer-reviewed], [Invited]
Japanese, Scientific journal

Pd-Catalyzed Allylic Isocycnation: Nucleophilic N-Terminus Substitution of Ambident Cyanide　　　　　　　　　　　　　　　
Taiga Yurino, Ryutaro Tani, Takeshi Ohkuma
ACS Catalysis, 9, 4434, 4440, Apr. 2019, [Peer-reviewed]
English, Scientific journal

Development of Highly Active Hydrogenation Catalysts　　　　　　　　　　　　　　　
Takeshi Ohkuma
Chemistry & Chemical Industry, 72, 3, 259, 261, Mar. 2019, [Peer-reviewed], [Invited]
Japanese, Scientific journal

Development of Asymmetric Reactions Catalyzed by Ruthenium Complexes with Two Kinds of Ligands
T. Ohkuma, N. Kurono, N. Arai
Bulletin of the Chemical Society of Japan, 92, 3, 475, 504, Dec. 2018, [Peer-reviewed], [Invited]
English, Scientific journal, © 2019 The Chemical Society of Japan. All rights reserved. Two types of chiral Ru(II) complexes, each with two kinds of ligands, have been designed and utilized as catalysts for several asymmetric reactions under appropriate conditions. The first type, the diphosphine/diamineRu(II)-type complexes, were found to catalyze the hydrogenation of a variety of simple and functionalized ketones as well as imino compounds with high activity and enantioselectivity. The double asymmetric hydrogenation of α,β-unsaturated ketones into the chiral saturated alcohols was achieved by using the dual catalyst system, which reversibly forms two catalytic species. The asymmetric isomerization of primary allylic alcohols into the optically active aldehydes with almost perfect enantioselectivity was realized with this type of catalyst. The second type, the amino acid/diphosphineRu(II)-type complexes combined with Li compounds, exhibited excellent catalyst performance in the asymmetric cyanosilylation of aldehydes as well as simple and functionalized ketones. The isolated Ru¢Li bimetallic complexes were suitable for the asymmetric hydrocyanation of aldehydes. This combined system was applicable to the asymmetric conjugate hydrocyanation of α,β-unsaturated ketones and carboxylic acid derivatives, and the Strecker-type reaction of the π-isoelectronic N-alkoxycarbonyl aldimines. This account describes the concept underlying the design of these catalysts, and the catalyst performance in the asymmetric reactions.

Asymmetric Hydrogenation of Polysubstituted Aromatic Ketones Catalyzed by the DIPSkewphos/PICA Derivative–Ruthenium(II) Complexes　　　　　　　　　　　　　　　
N. Utsumi, N. Arai, K. Kawaguchi, T. Katayama, T. Yasuda, K. Murata, T. Ohkuma
ChmCatChem, 10, 3955, 3959, Jul. 2018, [Peer-reviewed]
English, Scientific journal

Enantioselective Cyanosilylation of Alkynyl Ketones Catalyzed by Combined Systems Consisting of Chiral Ruthenium(II) Complex and Lithium Phenoxide
Takeshi Ohkuma, Nobuhito Kurono, Yusuke Sakaguchi, Kohei Yamauchi, Taiga Yurino
Advanced Synthesis and Catalysis, 360, 7, 1517, 1522, Wiley-VCH Verlag, 03 Apr. 2018, [Peer-reviewed]
English, Scientific journal, Asymmetric cyanosilylation of alkynyl ketones with the catalyst systems consisting of amino acid/2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP)/ruthenium(II) complex and lithium phenoxide (Ru⋅Li cat.) was studied. The reaction was conducted in tert-butyl methyl ether (TBME) at −78 °C with a substrate-to-catalyst molar ratio (S/C) as high as 2000. A series of simple and functionalized ketones was converted into the alkynyl tertiary cyanohydrin derivatives in up to 99% ee. Appropriate selection of an amino-acid ligand of the catalyst according to the substrate structure was crucially important to achieve high enantioselectivity and a wide scope of substrates. Transformation of the chiral cyanohydrin product into a functionalized lactone was also examined. (Figure presented.).

Construction of Unique Heterocyclic Frameworks by Photochemical Reaction of 5- and 6-Membered Heteroaromatics　　　　　　　　　　　　　　　
N. Arai, T. Ohkuma
Heterocycles, 96, 6, 997, 1035, Mar. 2018, [Peer-reviewed], [Invited]
English, Scientific journal

Chemoselectivity Control in the Asymmetric Hydrogenation of γ- and δ-Keto Esters into Hydroxy Esters or Diols
Noriyoshi Arai, Takanori Namba, Kei Kawaguchi, Yuki Matsumoto, Takeshi Ohkuma
Angewandte Chemie - International Edition, 57, 5, 1386, 1389, Wiley-VCH Verlag, 26 Jan. 2018, [Peer-reviewed]
English, Scientific journal, The asymmetric hydrogenation of aromatic γ- and δ-keto esters into optically active hydroxy esters or diols under the catalysis of a novel DIPSkewphos/3-AMIQ–RuII complex was studied. Under the optimized conditions (8 atm H2, Ru complex/t-C4H9OK=1:3.5, 25 °C) the γ- and δ-hydroxy esters (including γ-lactones) were obtained quantitatively with 97–99 % ee. When the reaction was conducted under somewhat harsh conditions (20 atm H2, [t-C4H9OK]=50 mm, 40 °C), the 1,4- and 1,5-diols were obtained predominantly with 95–99 % ee. The reactivity of the ester group was notably dependent on the length of the carbon spacer between the two carbonyl moieties of the substrate. The reaction of β- and ϵ-keto esters selectively afforded the hydroxy esters regardless of the reaction conditions. This catalyst system was applied to the enantioselective and regioselective (for one of the two ester groups) hydrogenation of a γ-ϵ-diketo diester into a trihydroxy ester.

Chiraltechnology　　　　　　　　　　　　　　　
OHKUMA Takeshi
Chemical Engineering Japan, 81, 12, 666, 669, Dec. 2017, [Peer-reviewed], [Invited]
Japanese, Scientific journal

Synthetic Organic Chemistry (2)
N. Arai, T. Ohkuma
Chemistry Today, 12, 18, 23, 東京化学同人, Dec. 2017, [Peer-reviewed], [Invited]
Japanese, Scientific journal

Synthetic Organic Chemistry (1)
N. Arai, T. Ohkuma
Chemistry Today, 11, 17, 21, 東京化学同人, Nov. 2017, [Peer-reviewed], [Invited]
Japanese, Scientific journal

Photochemically Promoted Aza-Diels-Alder-Type Reaction: High Catalytic Activity of the Cr(III)/Bipyridine Complex Enhanced by Visible Light Irradiation
Noriyoshi Arai, Takeshi Ohkuma
Journal of Organic Chemistry, 82, 14, 7628, 7636, American Chemical Society, 21 Jul. 2017, [Peer-reviewed]
English, Scientific journal, Aza-Diels-Alder-type cycloaddition reactions between a range of N-arylimines and functionalized alkenes were effectively catalyzed by the Cr(III)/bipyridine complex under irradiation of blue light, to give the corresponding 1,2,3,4-tetrahydroquinoline derivatives in high yields with excellent diastereoselectivity. Typically, the reaction of benzylideneaniline with 1-vinyl-2-pyrrolidinone proceeded smoothly with a substrate-to-catalyst molar ratio (S/C) of 1000 and completed within 4 h at room temperature (20-25 °C), affording the cycloaddition product in 97% yield.

Double Asymmetric Hydrogenation of Linear beta,beta-Disubstituted alpha,beta-Unsaturated Ketones into gamma-Substituted Secondary Alcohols using a Dual Catalytic System
Noriyoshi Arai, Hironori Satoh, Ryo Komatsu, Takeshi Ohkuma
CHEMISTRY-A EUROPEAN JOURNAL, 23, 37, 8806, 8809, WILEY-V C H VERLAG GMBH, Jul. 2017, [Peer-reviewed]
English, Scientific journal, Double asymmetric hydrogenation of linear beta,beta-disubstituted alpha,beta-unsaturated ketones catalyzed by the DM-SEGPHOS/DMAPEN/Ru-II complex with t-C4H9OK afforded the gamma-substituted secondary alcohols in high diastereo-and enantioselectivities. Some mechanistic experiments suggested that two different reactive species, type (I) and (II), were reversibly formed in this catalytic system: Type (I) with the diamine ligand DMAPEN enantioselectively hydrogenated the enones into the chiral allylic alcohols, and type (II) without the diamine ligand diastereoselectively hydrogenated the allylic alcohols into the gamma-substituted secondary alcohols. This dual catalysis protocol was successfully applied to the reaction of a variety of aliphatic-and aromatic-substituted enone substrates.

Special Issue Dedicated to Professor Ryoji Noyori on the 15th Anniversary of His Nobel Prize in Chemistry: Introductory Remarks
Takeshi Ohkuma
CHEMICAL RECORD, 16, 6, 2428, 2429, WILEY-V C H VERLAG GMBH, Dec. 2016, [Peer-reviewed], [Invited]
English, Scientific journal

Advancement in Catalytic Asymmetric Hydrogenation of Ketones and Imines, and Development of Asymmetric Isomerization of Allylic Alcohols
Takeshi Ohkuma, Noriyoshi Arai
CHEMICAL RECORD, 16, 6, 2801, 2819, WILEY-V C H VERLAG GMBH, Dec. 2016, [Peer-reviewed], [Invited]
English, Scientific journal, Catalytic asymmetric hydrogenation of ketones through the "metal-ligand cooperative mechanism" has been improved in terms of the efficiency, stereoselectivity, and scope of substrates by varying the arrangement of the catalyst structure and reaction conditions. Imino compounds are also smoothly converted to the optically active amines with appropriate catalysts. This type of catalyst exhibits excellent performance on the asymmetric isomerization of primary allylic alcohols into the optically active aldehydes. This personal account describes recent progress on these topics.

Efficient chemoselective hydrogenation of organic azides catalyzed by palladium nanoparticles with alkyne-derived homogeneous supports
Noriyoshi Arai, Nozomi Onodera, Takeshi Ohkuma
TETRAHEDRON LETTERS, 57, 37, 4183, 4186, PERGAMON-ELSEVIER SCIENCE LTD, Sep. 2016, [Peer-reviewed]
English, Scientific journal, Catalytic chemoselective hydrogenation of organic azides using palladium nanoparticles stabilized by alkyne derivatives was studied. A broad range of aromatic and aliphatic azides were smoothly reduced to the corresponding amines in excellent yields with a quite small amount of the catalyst. Hydrogenation of 3-phenylpropylazide gave 3-phenylpropylamine almost quantitatively with a substrate-to-palladium molar ratio (S/Pd) of 12,900 under 8 atm of H-2. The reaction under 1 atm of H2 also proceeded smoothly with an S/Pd of 1000. Several reduction-sensitive functional groups, such as carbonyl, halide, benzylic OH, and aliphatic nitro were well tolerated under the reaction conditions. (C) 2016 Elsevier Ltd. All rights reserved.

Development of Methods for Construction of Heterocyclic Frameworks by Photochemical Activation of Molecules
Noriyoshi Arai, Takeshi Ohkuma
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN, 74, 4, 360, 371, SOC SYNTHETIC ORGANIC CHEM JPN, Apr. 2016, [Peer-reviewed], [Invited]
Japanese, Scientific journal, Novel methods for the construction of molecular frameworks were developed by means of photochemical activation of 5-membered heteroaromatics, including furans, thiophenes, thiazoles, and oxazoles. Intramolecular Diels-Alder-type cycloaddition reactions between furan and an unactivated alkene moiety were found to proceed in high yields in the presence of 9,10-dicyanoanthracene under UV irradiation to afford oxabicyclo[2.2.1]heptane derivatives with high stereoselectivity. Photoirradiation onto alpha-arylthiophene derivatives linked with an alkene moiety through a three-atom spacer gave unprecedented cyclobutene-fused perhydrothiapentalene-type compounds in high yields with high stereoselectivity. A photo-ene type cyclization of 2-aryloxazole derivatives linked with an alkene moiety through a three-atom spacer at the 5-position gave a range of functionalized spiro[4.4] cyclic compounds that included cyclopentane, tetrahydrofuran, and pyrrolidine moieties in moderate to high yields with excellent diastereoselectivity.

Catalytic Asymmetric Cyanation Reactions
Nobuhito Kurono, Takeshi Ohkuma
ACS CATALYSIS, 6, 2, 989, 1023, AMER CHEMICAL SOC, Feb. 2016, [Peer-reviewed], [Invited]
English, Scientific journal, Catalytic asymmetric cyanations of prochiral unsaturated compounds affording the corresponding nitrile products in high enantiomeric excess (>= 90% in general) are summarized in this review. The nucleophilic cyanide addition onto aldehydes, ketones, and imines is promoted by chiral metal complexes and organocatalysts. Recent progress in asymmetric conjugate cyanation of alpha,beta-unsaturated carbonyl compounds is also discussed. The asymmetric cyanation of unactivated alkenes is catalyzed by chiral transition-metal complexes. Current topics of intramolecular carbocyanation and aminocyanation in addition to the traditional hydrocyanation are reviewed.

Hydrogenation of nitroarenes with palladium nanoparticles stabilized by alkyne derivatives in homogeneous phase
Noriyoshi Arai, Nozomi Onodera, Atsushi Dekita, Junichi Hori, Takeshi Ohkuma
TETRAHEDRON LETTERS, 56, 25, 3913, 3915, PERGAMON-ELSEVIER SCIENCE LTD, Jun. 2015, [Peer-reviewed]
English, Scientific journal, Palladium nanoparticles stabilized by alkyne derivatives catalyzed the hydrogenation of nitroarenes to the aryl amines in homogeneous phase. The reaction of nitrobenzene proceeded smoothly with a substrate-to-palladium molar ratio (S/Pd) of 51,000 under 8 atm of H-2. The reaction under 1 atm of H-2 with an S/Pd of 1030 was completed in 4 h. A series of substituted nitroarenes, including 4-acetyl- and 4-formylnitrobenzenes, were converted to the aryl amines with high chemoselectivity. (C) 2015 Elsevier Ltd. All rights reserved.

Asymmetric Hydrogenation of Ketones and Imines Catalyzed by Ru(II) Complexes　　　　　　　　　　　　　　　
OHKUMA Takeshi
Pharmacia, 51, 4, 295, 299, Apr. 2015, [Peer-reviewed]
Japanese, Scientific journal

Stereoselective Preparation of Spiro[4.4] Cyclic Compounds by the Photochemical Activation of Oxazoles
Noriyoshi Arai, Moe Mizota, Takeshi Ohkuma
ORGANIC LETTERS, 17, 1, 86, 89, AMER CHEMICAL SOC, Jan. 2015, [Peer-reviewed]
English, Scientific journal, A novel photocyclization of 2-aryloxazole derivatives linked with an alkene moiety through a three-atom spacer at the 5-position gave a range of functionalized spiro[4.4] cyclic compounds that included cyclopentane, tetrahydrofuran, and pyrrolidine moieties in moderate to high yields with excellent diastereoselectivity.

NOVEL INTRAMOLECULAR CYCLIZATION-SKELETAL REORGANIZATION OF 2-ARYLTHIAZOLES UNDER PHOTOIRRADIATION
Noriyoshi Arai, Moe Mizota, Takeshi Ohkuma
HETEROCYCLES, 90, 1, 607, 616, PERGAMON-ELSEVIER SCIENCE LTD, Jan. 2015, [Peer-reviewed], [Invited]
English, Scientific journal, Photoirradiation of 2-arylthiazoles derivatives linked with an alkene moiety through a three-atom spacer was investigated. The main products were unexpected tetrahydrofuran-fused thiazepine derivatives with concomitant formation of [2+2] cycloaddition products and regioisomeric thiazoles. The product distribution was little influenced by the reaction conditions and substituents of the substrates.

Asymmetric Conjugate Hydrocyanation of alpha,beta-Unsaturated N-Acylpyrroles with the Ru(phgly)(2)(binap)-CH3OLi Catalyst System
Yusuke Sakaguchi, Nobuhito Kurono, Kohei Yamauchi, Takeshi Ohkuma
ORGANIC LETTERS, 16, 3, 808, 811, AMER CHEMICAL SOC, Feb. 2014, [Peer-reviewed]
English, Scientific journal, Asymmetric conjugate hydrocyanation of alpha,beta-unsaturated carboxylic acid derivatives catalyzed by a Ru[ (S)phgly](2)[ (S)-binap]-CH2OLi system was examined. The N-acylpyrrole gave the best result in terms of reactivity and enantioselectivity. A series of substrates with alkyl or heterosubstituted alkyl groups at the beta-position reacted with a substrate-to-catalyst molar ratio of 200-2000 to afford the beta-cyano products in the range of 88%->99% ee. The mode of enantioselection in the hydrocyanation was proposed.

Enantioselective Isomerization of Primary Allylic Alcohols into Chiral Aldehydes with the tol-binap/dbapen/Ruthenium(II) Catalyst
Noriyoshi Arai, Keisuke Sato, Keita Azuma, Takeshi Ohkuma
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 52, 29, 7500, 7504, WILEY-V C H VERLAG GMBH, Jul. 2013, [Peer-reviewed]
English, Scientific journal

Asymmetric Hydrogenation of Alkynyl Ketones with the eta(6)-Arene/TsDPEN-Ruthenium(II) Catalyst
Noriyoshi Arai, Hironori Satoh, Noriyuki Utsumi, Kunihiko Murata, Kunihiko Tsutsumi, Takeshi Ohkuma
ORGANIC LETTERS, 15, 12, 3030, 3033, AMER CHEMICAL SOC, Jun. 2013, [Peer-reviewed]
English, Scientific journal, Enantioselective hydrogenation of alkynyl ketones catalyzed by Ru(OTf)(TsDPEN)(eta(6)-p-cymene) (TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine) affords the propargylic alcohols in up to 97% ee. The alkynyl moieties are left intact In most cases. The reaction can be conducted with a substrate-to-catalyst molar ratio as high as 5000 under 10 atm of H-2. The mode of enantioselection is elucidated with the transition state models directed by the CH/pi attractive interaction between the substrate and the catalytic species.

Preparation of Diastereomerically Pure and Mixed (S)-PhGly/BIPHEP/Ru(II) Complexes and Their Catalytic Behavior with Li2CO3 in Asymmetric Cyanosilylation of Benzaldehyde
Nobuhito Kurono, Taiki Katayama, Takeshi Ohkuma
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 86, 5, 577, 582, CHEMICAL SOC JAPAN, May 2013, [Peer-reviewed]
English, Scientific journal, A diastereomerically mixed complex [Ru{(S)-phgly}(2){(+/-)-biphep}] is readily prepared from achiral diphosphine BIPHEP in two steps. These diastereomers are then separated by silica gel column chromatography. A 61:39 equilibrium mixture of [Ru{(S)-phgly}(2){(S)-biphep}] and [Ru{(S)-phgly}(2){(R)-biphep}] with Li2CO3 is used to catalyze cyano-silylation of benzaldehyde to afford the R cyanated product in 92% ee. The enantioselectivity is just slightly lower than that by using the pure [Ru{(S)-phgly}(2){(S)-biphep}]/Li2CO3 catalyst system of 96%. The high enantioselective ability of the diastereomerically mixed catalyst is revealed through a series of kinetic experiments in which the highly enantioselective [Ru{(S)-phgly}(2){(S)-biphep}]/Li2CO3 system is shown to catalyze the reaction 16.8 times faster than the less selective [Ru{(S)-phgly}(2){(R)-biphep}]/Li2CO3 system, affording the product in 2.6% ee. An equation is derived to approximate the relationship between the diastereomeric ratio of the catalyst and the ee value of the product.

Synthesis of 8-Oxoberbines and Related Benzolactams by Pd(OAc)2-Catalyzed Direct Aromatic Carbonylation
Mamoru Miyazawa, Takashi Tokuhashi, Akiyoshi Horibata, Takatoshi Nakamura, Yu Onozaki, Nobuhito Kurono, Hisanori Senboku, Masao Tokuda, Takeshi Ohkuma, Kazuhiko Orito
JOURNAL OF HETEROCYCLIC CHEMISTRY, 50, E48, E54, WILEY-BLACKWELL, Feb. 2013, [Peer-reviewed]
English, Scientific journal, A variety of alkoxy-substituted benzolactams with a berbine or yohimbane skeleton were prepared from 1-benzyl-1,2,3,4-tetrahydroisoquinolines or 1-benzyl-1,2,3,4-tetrahydro-beta-carbolines by a phosphine-free Pd(II)-catalyzed direct aromatic carbonylation in a Pd(OAc)(2)-Cu(OAc)(2) catalytic system. The site selectivity was compared with that of the carbonylation with Pd(OAc)(2) or Pd(OAc)(2)center dot 2 PPh3, respectively.

Asymmetric hydrogenation of quinoxalines, benzoxazines, and a benzothiazine catalyzed by chiral ruthenabicyclic complexes
Noriyoshi Arai, Yu Saruwatari, Kotaro Isobe, Takeshi Ohkuma
Advanced Synthesis and Catalysis, 355, 14-15, 2769, 2774, Wiley-VCH Verlag, 2013, [Peer-reviewed]
English, Scientific journal, The ruthenabicyclic complex RuCl[ (R)-daipena][ (R)-dm-segphos] with potassium tert-butoxide catalyzes the hydrogenation of 2-alkylquinoxalines and a 3-methyl-2H-1,4-benzoxazine in toluene under 20-100 atm of hydrogen at 40 °C to afford S-configured cyclic amino products in greater than 97% enantiomeric excess {DAIPENA=anion of DAIPEN at the 2-position of an anisyl group, DAIPEN=1,1-di (4-anisyl)-2-isopropyl-1,2-ethylenediamine, DM-SEGPHOS=(4,4′-bi-1,3-benzodioxole)-5,5′-diylbis[di(3,5-xylyl) phosphine]}. The high catalytic activity results in a turnover number as high as 9400. Hydrogenation of the benzoimine heterocycles with the RuCl[ (R)-daipena][ (R)-segphos]/ potassium tert-butoxide system yields the R-configured products in high enantiomeric excess [SEGPHOS=(4,4′-bi-1,3- benzodioxole)-5,5′-diylbis-(diphenylphosphine)]. The mode of enantioselection is discussed based on transition state models involving six-membered pericyclic structures. © 2013 Wiley-VCH Verlag GmbH&
Co. KGaA, Weinheim.

5.11 Reduction - Hydrogenation: C=O; Chemoselective
T. Ohkuma, N. Arai
Comprehensive Chirality, 5, 270, 300, Elsevier Ltd, Sep. 2012, [Peer-reviewed]
English, In book, In this chapter asymmetric hydrogenation of ketones by the use of chiral catalysts is described. In the first part, the asymmetric hydrogenation of functionalized ketones including β-keto esters, α-keto esters, and α-alkoxy or amino ketones is discussed mainly in homogeneous catalytic systems. In the second part, we describe the highly stereoselective manner of the reaction with nonfunctionalized (simple) ketones. The final part of this chapter deals with the highly diastereo- and enantioselective hydrogenation accompanied by dynamic kinetic resolution. © 2012 Elsevier Ltd. All rights reserved.

Asymmetric Cyanation with the Chiral Ru-Li Combined Catalysts
Takeshi Ohkuma, Nobuhito Kurono
SYNLETT, 23, 13, 1865, 1881, GEORG THIEME VERLAG KG, Aug. 2012, [Peer-reviewed]
English, Scientific journal, The combined systems of phenylglycinate/BINAP/Ru(II) complex and Li compounds have been found to act as highly reactive and enantioselective catalysts for cyanosilylation and hydrocyanation of aldehydes, alpha-keto esters, alpha,beta-unsaturated ketones, and N-protected aldimines. In this account, we describe the concept of catalyst design, the catalytic efficiency of the novel combined systems in the asymmetric cyanation, and the proposed reaction pathway based on the spectral analysis data.
1 Introduction
2 Cyanosilylation of Aldehydes and Ketones Catalyzed by LiCl
3 Asymmetric Cyanosilylation of Aldehydes and alpha-Keto Esters
3.1 Design of Chiral Ru-Li Combined Catalyst Systems
3.2 Cyanosilylation of Aldehydes
3.3 Cyanosilylation of alpha-Keto Esters
4 Asymmetric Hydrocyanation of Aldehydes, alpha,beta-Unsaturated Ketones, and Aldimines
4.1 Hydrocyanation of Aldehydes
4.2 Conjugate Cyanation of alpha,beta-Unsaturated Ketones
4.3 Strecker-Type Reaction
5 Mechanistic Considerations for Cyanosilylation of Aldehydes and Ketones
5.1 Achiral Reaction Catalyzed by LiCl
5.2 Asymmetric Reaction with the Chiral Ru-Li Combined Catalyst
6 Conclusion

Asymmetric Hydrogenation of N-Arylimines Catalyzed by the Xyl-Skewphos/DPEN-Ruthenium(II) Complex
Noriyoshi Arai, Noriyuki Utsumi, Yuki Matsumoto, Kunihiko Murata, Kunihiko Tsutsumi, Takeshi Ohkuma
ADVANCED SYNTHESIS & CATALYSIS, 354, 11-12, 2089, 2095, WILEY-V C H VERLAG GMBH, Aug. 2012, [Peer-reviewed]
English, Scientific journal, The new catalyst system of RuBr2[ (S,S)-xyl-skewphos][ (S,S)-dpen] and potassium tert-butoxide shows high reactivity and enantioselectivity in the hydrogenation of N-arylimines [Xyl-Skewphos=2,4-bis(di-3,5-xylylphosphino)pentane, DPEN=1,2-diphenylethylenediamine]. A range of imines derived from aromatic and heteroaromatic ketones as well as some ferrocenyl and vinylic imines are hydrogenated with a turnover number as high as 18,000 under 10-50 atm of hydrogen to afford the amine products in up to 99% enantiomeric excess. The reaction is applied to the synthesis of a chiral N-arylamine, which is the synthetic intermediate of a biologically active compound. The mode of enantioselection is interpreted by using transition-state models based on the X-ray structure of the Xyl-Skewphos/DPEN-RuBr2 complex.

Synthesis of Benzo[c]phenanthridine Alkaloids by Pd(OAc)2-Induced Direct Aromatic Carbonylation
Eri Kumazawa, Takashi Tokuhashi, Akiyoshi Horibata, Nobuhito Kurono, Hisanori Senboku, Masao Tokuda, Takashi Ohkuma, Kazuhiko Orito
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2012, 24, 4622, 4633, WILEY-V C H VERLAG GMBH, Aug. 2012, [Peer-reviewed]
English, Scientific journal, The Pd(OAc)2-induced carbonylation of alkoxy-substituted 1-amino-2-phenyltetralins and 1-amino-2-phenylnaphthalenes was examined to provide the benzo[c]phenanthridine ring system. The carbonylation of substrates containing methylenedioxy groups gave oxysanguinarine and oxyavicine. The tetramethoxy derivatives gave O-methyloxyfagaronine. The substrate with a benzyloxy group afforded a known synthetic precursor to the antileukemic alkaloid, fagaronine.

ルテナビシクロ錯体触媒を用いたキノキサリン類の不斉水素化反応
新井則義, 猿渡佑, 磯部孝太郎, 大熊毅
万有生命科学振興国際交流財団札幌シンポジウム, 24th, 45, 07 Jul. 2012
Japanese

Enantioselective Cyanosilylation of Ketones with Amino Acid/BINAP/Ruthenium(II)-Lithium Phenoxide Catalyst Systems
Masato Uemura, Nobuhito Kurono, Yusuke Sakai, Takeshi Ohkuma
ADVANCED SYNTHESIS & CATALYSIS, 354, 10, 2023, 2030, WILEY-V C H VERLAG GMBH, Jul. 2012, [Peer-reviewed]
English, Scientific journal, Enantioselective reactions of simple ketones, a,a- and beta,beta-dialkoxy ketones, and a-alkoxy ketones with trimethylsilyl cyanide catalyzed by the bimetallic systems of amino acid/BINAP/ruthenium(II) complexes and lithium phenoxide have been studied [BINAP=2,2'-bis(diphenylphosphino)-1,1'-binaphthyl]. The Ru(PhGly)2(BINAP)-lithium phenoxide system showed high enantioselectivity for the reaction of acetophenone derivatives to afford the cyanated products in up to 90% ee [PhGly=phenylglycinate]. For the cyanosilylation of dialkoxy ketones and a-alkoxy ketones, the Ru(t-Leu)2(BINAP)-lithium phenoxide system exhibited the best catalyst performance to produce the cyanohydrin derivatives in up to 99% ee and 98% ee, respectively [t-Leu=tert-leucinate]. The excellent catalytic activity resulted in complete conversion in the reaction with a substrate-to-catalyst molar ratio (S/C) of 10,000 in the best cases.

Synthesis of a 3-Arylisoquinoline Alkajoid, Decumbenine B.　　　　　　　　　　　　　　　
Kumazawa E, Tokuhashi T, Horibata A, Kurono N, Senboku H, Tokuda M, Ohkuma T, Orito K
European Journal of Organic Chemistry, 4622, 4633, Jul. 2012, [Peer-reviewed]
English, Scientific journal

Design of molecular catalysts for achievement of high turnover number in homogeneous hydrogenation.
Arai N, Ohkuma T
Chemical record (New York, N.Y.), 12, 2, 284, 289, 2, Apr. 2012, [Peer-reviewed]

新規なルテナビシクロ錯体触媒(RUCY)によるケトン類の高速かつ高選択的不斉水素化反応
松村和彦, 新井則義, 堀清人, 齊藤隆夫, 佐用昇, 大熊毅
日本化学会講演予稿集, 92nd, 2, 342, 09 Mar. 2012
Japanese

α‐アリールチオフェン類の新規分子内光環化反応
新井則義, 田中皓一郎, 大熊毅
日本化学会講演予稿集, 92nd, 4, 1243, 09 Mar. 2012
Japanese

ルテニウム錯体触媒によるN‐アリールイミン類の不斉水素化反応
内海典之, 新井則義, 松本祐樹, 村田邦彦, 堤邦彦, 大熊毅
日本化学会講演予稿集, 92nd, 4, 1463, 09 Mar. 2012
Japanese

飽和複素環ケトン類の不斉水素化:触媒制御によるジアステレオ選択
明石真也, 新井則義, 井上勉, 大熊毅
日本化学会講演予稿集, 92nd, 4, 1463, 09 Mar. 2012
Japanese

ルテニウム/リチウム複合錯体触媒を用いるアルジミン類の不斉ヒドロシアノ化反応
植村真人, 黒野暢仁, 大熊毅
日本化学会講演予稿集, 92nd, 4, 1381, 09 Mar. 2012
Japanese

Novel Intramolecular Photocyclization of alpha-Arylthiophene Derivatives
Noriyoshi Arai, Koichiro Tanaka, Takeshi Ohkuma
ORGANIC LETTERS, 14, 6, 1488, 1491, AMER CHEMICAL SOC, Mar. 2012, [Peer-reviewed]
English, Scientific journal, Photoirradiation of alpha-arylthiophene derivatives linked with an alkene moiety through a three-atom spacer gave unprecedented cyclobutene-fused perhydrothiapentalene-type compounds in high yields, but neither [2 + 2] nor [4 + 2] cycloaddition products. The reaction afforded a single diastereomer in many cases. The chemical structure and relative configuration of a typical product were unambiguously determined by X-ray crystallographic analysis.

Enantioselective Hydrocyanation of N-Protected Aldimines
Masato Uemura, Nobuhito Kurono, Takeshi Ohkuma
ORGANIC LETTERS, 14, 3, 882, 885, AMER CHEMICAL SOC, Feb. 2012, [Peer-reviewed]
English, Scientific journal, Enantioselective hydrocyanation of N-benzyloxycarbonyl aldimines catalyzed by a Ru[ (S)-phgly](2)[ (S)-binap]/C6H5OLi system or a bimetallic complex [Li{Ru[ (S)-phgly](2)[ (S)-binap]}]Cl affords the amino nitriles in 92-99% ee. The reaction is carried out in tert-C4H9OCH3 with a substrate-to-catalyst molar ratio in the range of 500-5000 at -20 to 0 degrees C. Primary, secondary, and tertiary alkyl imines as well as the aryl and heteroaryl substrates are smoothly cyanated to produce the desired products in high yield.

Phosphane-Free Pd-0-Catalyzed Cycloamination and Carbonylation with Pd(OAc)(2) and Cu(OAc)(2) in the Presence of K2CO3: Preparation of Benzocyclic Amines and Benzolactams
Rika Harada, Naoto Nishida, Shiho Uchiito, Yu Onozaki, Nobuhito Kurono, Hisanori Senboku, Tokuda Masao, Takeshi Ohkuma, Kazuhiko Orito
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2012, 2, 366, 379, WILEY-V C H VERLAG GMBH, Jan. 2012, [Peer-reviewed]
English, Scientific journal, Phosphane-free Pd-0-catalyzed intramolecular aromatic amination was studied. o-Halophenethylamines and 3-(o-halophenyl)propylamines were found to be transformed into indolines and quinolines in a catalytic system based on Pd(OAc)(2) and Cu(OAc)(2) in the presence of K2CO3. Application of the method to substrates containing isoquinoline rings - the 1-(o-bromobenzyl)-3,4-dihydroisoquinolines 6, the 1-(o-bromobenzyl)-1,2,3,4-tetrahydroisoquinolines 7, and the 1-(o-bromophenethyl)isoquinolines 9 - provided the indolo[2,1-a] isoquinoline and dibenzo[a,f] quinolizine ring systems 8 and 10. Extension of the method to beta-carbolines (compounds 11, 12, and 17) produced the benz[f] indolo[2,3-a]indolizine-13-ones 15 and the benz[f] indolo[2,3-a] quinolizine 18. The benzo[f] pyrido[3,4-a] indolizine and indolo[f] pyrido[ 3,4-a]indolizin-12-one ring systems 27 and 31 were built in a similar manner. It was also found that under an atmosphere of CO the same catalytic system produced the corresponding benzolactams, the isoquino[2,1-a][2,7] naphthyridine 34 and the indolo[2,3-a] pyrido[g]quinolizin-8-one 36 [ (+/-)-dihydronauclefine] in good yields.

Kinetic Resolution of Racemic alpha-tert-Alkyl-alpha-hydroxy Esters by Enantiomer-Selective Carbamoylation
Nobuhito Kurono, Kentaro Ohtsuga, Masanori Wakabayashi, Tadahiro Kondo, Hirohito Ooka, Takeshi Ohkuma
JOURNAL OF ORGANIC CHEMISTRY, 76, 24, 10312, 10318, AMER CHEMICAL SOC, Dec. 2011
English, Scientific journal, Kinetic resolution of sterically hindered racemic alpha-tert-alkyl-alpha-hydroxy esters is performed by enantiomer-selective carbamoylation with the t-Bu-Box-Cu(II) catalyst (Box = bis(oxazoline)). The reaction with 0.5 equiv of n-C3H7NCO is carried out with a substrate-to-catalyst molar ratio of 500-5000 at -20 to 25 degrees C. The high enantiomer-discrimination ability of the catalyst achieves an excellent stereoselectivity factor (s = k(fast)/k(slow)) of 261 in the best case. A catalytic cycle for this reaction is proposed.

Kinetic Resolution of Racemic alpha-tert-Alkyl-alpha-hydroxy Esters by Enantiomer-Selective Carbamoylation
Nobuhito Kurono, Kentaro Ohtsuga, Masanori Wakabayashi, Tadahiro Kondo, Hirohito Ooka, Takeshi Ohkuma
JOURNAL OF ORGANIC CHEMISTRY, 76, 24, 10312, 10318, AMER CHEMICAL SOC, Dec. 2011, [Peer-reviewed]
English, Scientific journal, Kinetic resolution of sterically hindered racemic alpha-tert-alkyl-alpha-hydroxy esters is performed by enantiomer-selective carbamoylation with the t-Bu-Box-Cu(II) catalyst (Box = bis(oxazoline)). The reaction with 0.5 equiv of n-C3H7NCO is carried out with a substrate-to-catalyst molar ratio of 500-5000 at -20 to 25 degrees C. The high enantiomer-discrimination ability of the catalyst achieves an excellent stereoselectivity factor (s = k(fast)/k(slow)) of 261 in the best case. A catalytic cycle for this reaction is proposed.

Catalyst-Controlled Diastereoselection in the Hydrogenation of Heterocycloalkyl Ketones
Masaya Akashi, Noriyoshi Arai, Tsutomu Inoue, Takeshi Ohkuma
ADVANCED SYNTHESIS & CATALYSIS, 353, 11-12, 1955, 1960, WILEY-BLACKWELL, Aug. 2011
English, Scientific journal, alpha-Substituted chiral ketones that have small steric and electronic differences around the reaction sites are difficult substrates to reduce with high diastereoselectivity. Metal hydride reduction of 2-(4-benzoylmorpholinyl) phenyl ketone and 3-(1-tert-butoxycarbonylpiperidinyl) phenyl ketone using sodium borohydride, zinc borohydride, and potassium tri-sec-butylborohydride as reducing agents affords the syn- and anti-alcohols in a lower than 80:20 ratio. Hydrogenation of these ketones with a catalyst system of RuCl(2)(BIPHEP) (DMEN) and potassium tert-butoxide in 2-propanol results in the syn-alcohols with >= 99:1 selectivity [BIPHEP= 2,2'-bis(diphenylphosphino)biphenyl, DMEN= N,N-dimethylethylenediamine]. The marked difference in the diastereoselectivity suggests that the stereoselection in this hydrogenation is primarily regulated by the structure of the catalyst's reaction field ("catalyst-controlled diastereoselection") but not the internal stereocontrol of the substrates. This chemistry is applied to the asymmetric hydrogenation through dynamic kinetic resolution with a RuCl(2)[ (S)-BINAP][ (R)-DMAPEN]/potassium tert-butoxide catalyst [BINAP= 2,2'-bis(diphenylphosphino)- 1,1'-binaphthyl, DMAPEN = 2-dimethylamino-1-phenylethylamine]. A series of aryl heterocycloalkyl ketones has been converted to the alcohols in excellent diastereo- and enantioselectivities. The modes of catalyst-controlled diastereoselection and enantioselection are interpreted by using transition-state molecular models. (S,S)-Reboxetine, a selective norepinephrine uptake inhibitor, was synthesized from one of product alcohols.

ルテニウム錯体/C₆H₅OLi触媒系を用いるα,β‐不飽和ケトン類の不斉共役シアノ化反応
坂口祐亮, 新居紀之, 黒野暢仁, 大熊毅
万有生命科学振興国際交流財団札幌シンポジウム, 23rd, 54, 02 Jul. 2011
Japanese

Chiral Ruthenabicyclic Complexes: Precatalysts for Rapid, Enantioselective, and Wide-Scope Hydrogenation of Ketones
Kazuhiko Matsumura, Noriyoshi Arai, Kiyoto Hori, Takao Saito, Noboru Sayo, Takeshi Ohkuma
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 133, 28, 10696, 10699, AMER CHEMICAL SOC, Jul. 2011
English, Scientific journal, A novel ruthenabicyclic complex with base shows excellent catalytic activity in the asymmetric hydrogenation of ketones. The turnover frequency of the hydrogenation of acetophenone reaches about 35 000 min(-1) in the best case, affording 1-phenylethanol in >99% ee. Several aliphatic and base-labile ketones are smoothly converted to the corresponding alcohols in high enantioselectivity. The catalytic cycle for this hydrogenation, in which the ruthenabicyclic structure of the catalyst is maintained, is proposed on the basis of the deuteration experiment and spectroscopic analysis data.

ルテニウム錯体/C₆H₅OLi触媒系を用いるα,β‐不飽和ケトン類の不斉共役シアノ化反応
坂口祐亮, 新居紀之, 黒野暢仁, 大熊毅
日本化学会北海道支部夏季研究発表会講演要旨集, 2011, 15, 01 Jul. 2011
Japanese

Chiral Ruthenabicyclic Complexes: Precatalysts for Rapid, Enantioselective, and Wide-Scope Hydrogenation of Ketones
Kazuhiko Matsumura, Noriyoshi Arai, Kiyoto Hori, Takao Saito, Noboru Sayo, Takeshi Ohkuma
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 133, 28, 10696, 10699, AMER CHEMICAL SOC, Jul. 2011, [Peer-reviewed]
English, Scientific journal, A novel ruthenabicyclic complex with base shows excellent catalytic activity in the asymmetric hydrogenation of ketones. The turnover frequency of the hydrogenation of acetophenone reaches about 35 000 min(-1) in the best case, affording 1-phenylethanol in >99% ee. Several aliphatic and base-labile ketones are smoothly converted to the corresponding alcohols in high enantioselectivity. The catalytic cycle for this hydrogenation, in which the ruthenabicyclic structure of the catalyst is maintained, is proposed on the basis of the deuteration experiment and spectroscopic analysis data.

BINAP
Takeshi Ohkuma, Nobuhito Kurono
Privileged Chiral Ligands and Catalysts, 1, 53, Wiley-VCH, 07 Apr. 2011, [Peer-reviewed]
English, In book

BINAP/IPHAN‐Ru(II)錯体触媒によるビシクロケトン類の不斉水素化反応
新井則義, 明石真也, 杉崎聡, 大岡浩仁, 井上勉, 大熊毅
日本化学会講演予稿集, 91st, 4, 1256, 11 Mar. 2011
Japanese

ルテニウム錯体/C₆H₅OLi触媒系を用いるα,β‐不飽和ケトン類の不斉共役シアノ化反応
坂口祐亮, 新居紀之, 黒野暢仁, 大熊毅
日本化学会講演予稿集, 91st, 4, 1286, 11 Mar. 2011
Japanese

Cu(I)触媒による逆電子要請分子内イミニウムエン反応を用いた4‐アミノ‐3‐メチレンクロマン類の簡便合成
新井則義, 大熊毅
日本化学会講演予稿集, 91st, 4, 1203, 11 Mar. 2011
Japanese

ルテニウム‐リチウム複合錯体を用いるアルデヒド類の不斉ヒドロシアノ化反応
黒野暢仁, 吉川達也, 山崎幹緒, 大熊毅
日本化学会講演予稿集, 91st, 4, 1286, 11 Mar. 2011
Japanese

Enantioselective Hydrocyanation of Aldehydes Catalyzed by [Li{Ru(phgly)(2)(binap)}]X (X = Cl, Br)
Nobuhito Kurono, Tatsuya Yoshikawa, Mikio Yamasaki, Takeshi Ohkuma
ORGANIC LETTERS, 13, 5, 1254, 1257, AMER CHEMICAL SOC, Mar. 2011
English, Scientific journal, Novel bimetallic complexes [Li{Ru[ (S)-phgly](2)[ (S)-binap]}]X (X = Cl, Br) are readily synthesized by mixing Ru[ (S)-phgly](2)[ (S)-binap] and LiX. A single-crystal X-ray analysis reveals the structure. These bimetallic complexes efficiently catalyze asymmetric hydrocyanation of aldehydes with a substrate-to-catalyst molar ratio of 500-2000 at -78 to -60 degrees C. A range of aromatic, heteroaromatic, and alpha,beta-unsaturated aldehydes as well as a tert-alkyl aldehyde is converted to the cyanohydrins in high enantiomeric excess (up to 99%).

Intramolecular iminium ene reaction with Cu(I) catalysts: facile formation of 4-amino-3-methylenechromans from O-propargyl salicylaldehydes and dialkylamines
Noriyoshi Arai, Takeshi Ohkuma
TETRAHEDRON, 67, 9, 1617, 1622, PERGAMON-ELSEVIER SCIENCE LTD, Mar. 2011
English, Scientific journal, Reaction of O-propargyl salicylaldehyde and related compounds with dialkylamines in the presence of copper(I) iodide gave 4-(alkylamino)-3-methylenechroman derivatives in good yields through the loss of one alkyl group of the dialkylamine. The reaction also worked well by employing 2-amino benzaldehyde derivatives to afford 4-(alkylamino)-3-methylene-1,2,3,4-tetrahydroquinolines. A deuterium-labeling experiment suggested that the a-hydrogen of the dialkylamine was transferred intramolecularly into the terminal methylene. This result indicated the reaction mechanism, which involved the formation of iminium ion between the aldehyde and the dialkylamine followed by ene-type C-C bond formation with inverse electron demand and hydrolysis. (C) 2011 Elsevier Ltd. All rights reserved.

Enantioselective Hydrocyanation of Aldehydes Catalyzed by [Li{Ru(phgly)(2)(binap)}]X (X = Cl, Br)
Nobuhito Kurono, Tatsuya Yoshikawa, Mikio Yamasaki, Takeshi Ohkuma
ORGANIC LETTERS, 13, 5, 1254, 1257, AMER CHEMICAL SOC, Mar. 2011, [Peer-reviewed]
English, Scientific journal, Novel bimetallic complexes [Li{Ru[ (S)-phgly](2)[ (S)-binap]}]X (X = Cl, Br) are readily synthesized by mixing Ru[ (S)-phgly](2)[ (S)-binap] and LiX. A single-crystal X-ray analysis reveals the structure. These bimetallic complexes efficiently catalyze asymmetric hydrocyanation of aldehydes with a substrate-to-catalyst molar ratio of 500-2000 at -78 to -60 degrees C. A range of aromatic, heteroaromatic, and alpha,beta-unsaturated aldehydes as well as a tert-alkyl aldehyde is converted to the cyanohydrins in high enantiomeric excess (up to 99%).

Asymmetric Hydrocyanation of alpha,beta-Unsaturated Ketones into beta-Cyano Ketones with the [Ru(phgly)(2)(binap)]/C6H5OLi Catalyst System
Nobuhito Kurono, Noriyuki Nii, Yusuke Sakaguchi, Masato Uemura, Takeshi Ohkuma
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 50, 24, 5541, 5544, WILEY-BLACKWELL, 2011
English, Scientific journal

Asymmetric Hydrocyanation of alpha,beta-Unsaturated Ketones into beta-Cyano Ketones with the [Ru(phgly)(2)(binap)]/C6H5OLi Catalyst System
Nobuhito Kurono, Noriyuki Nii, Yusuke Sakaguchi, Masato Uemura, Takeshi Ohkuma
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 50, 24, 5541, 5544, WILEY-BLACKWELL, 2011, [Peer-reviewed]
English, Scientific journal

Asymmetric Hydrogenation of Bicyclic Ketones Catalyzed by BINAP/IPHAN-Ru(II) Complex
Noriyoshi Arai, Masaya Akashi, Satoshi Sugizaki, Hirohito Ooka, Tsutomu Inoue, Takeshi Ohkuma
ORGANIC LETTERS, 12, 15, 3380, 3383, AMER CHEMICAL SOC, Aug. 2010
English, Scientific journal, Hydrogenation of 3-quinuclidinone and bicyclo[2.2.2]octan-2-one with a combined catalyst system of RuCl(2)[ (S)-binap][ (R)-iphan] and t-C(4)H(9)OK in 2-propanol afforded the chiral alcohols in 97-98% ee. 2-Diphenylmethyl-3-quinuclidinone was hydrogenated with the same catalyst to the cis alcohol with perfect diastereo- and enantioselectivity. The reaction of unsymmetrical ketones with a bicyclo[2.2.1] or -[2.2.2] skeleton gave the corresponding alcohols with high stereoselectivity.

Asymmetric Hydrogenation of Bicyclic Ketones Catalyzed by BINAP/IPHAN-Ru(II) Complex
Noriyoshi Arai, Masaya Akashi, Satoshi Sugizaki, Hirohito Ooka, Tsutomu Inoue, Takeshi Ohkuma
ORGANIC LETTERS, 12, 15, 3380, 3383, AMER CHEMICAL SOC, Aug. 2010, [Peer-reviewed]
English, Scientific journal, Hydrogenation of 3-quinuclidinone and bicyclo[2.2.2]octan-2-one with a combined catalyst system of RuCl(2)[ (S)-binap][ (R)-iphan] and t-C(4)H(9)OK in 2-propanol afforded the chiral alcohols in 97-98% ee. 2-Diphenylmethyl-3-quinuclidinone was hydrogenated with the same catalyst to the cis alcohol with perfect diastereo- and enantioselectivity. The reaction of unsymmetrical ketones with a bicyclo[2.2.1] or -[2.2.2] skeleton gave the corresponding alcohols with high stereoselectivity.

フランと単純アルケンとの分子内光環化反応
新井則義, 田中皓一朗, 大熊毅
万有生命科学振興国際交流財団札幌シンポジウム, 22nd, 51, 03 Jul. 2010
Japanese

Xylskewphos/PICA‐ルテニウム錯体を触媒に用いる実用的な3‐キヌクリジノンの不斉水素化反応
堤邦彦, 大熊毅, 片山武昭, 内海典之, 村田邦彦, 新井則義, 黒野暢仁
日本化学会講演予稿集, 90th, 4, 1221, 12 Mar. 2010
Japanese

Ru(phgly)₂(binap)錯体を用いるα‐ケトエステル類の不斉シアノシリル化反応
黒野暢仁, 植村真人, 大熊毅
日本化学会講演予稿集, 90th, 4, 1221, 12 Mar. 2010
Japanese

フランと単純アルケンとの光増感分子内環化反応
新井則義, 田中皓一朗, 大熊毅
日本化学会講演予稿集, 90th, 4, 1281, 12 Mar. 2010
Japanese

パラジウムナノ粒子‐テトラブチルアンモニウムボロヒドリド触媒系によるアルキン類の高活性かつ高選択的な部分水素化反応
堀順一, 村田邦彦, 菅井俊樹, 篠原久典, 野依良治, 新井則義, 黒野暢仁, 大熊毅
日本化学会講演予稿集, 90th, 4, 1350, 12 Mar. 2010
Japanese

MsDPEN‐Cp^*イリジウム錯体触媒を用いる芳香族複素環状ケトン類の不斉水素化反応
内海典之, 大熊毅, 堤邦彦, 渡辺正人, 村田邦彦, 新井則義, 黒野暢仁
日本化学会講演予稿集, 90th, 4, 1215, 12 Mar. 2010
Japanese

Asymmetric hydrogenation of ketones: Tactics to achieve high reactivity, enantioselectivity, and wide scope
Takeshi Ohkuma
Proceedings of the Japan Academy Series B: Physical and Biological Sciences, 86, 3, 202, 219, Mar. 2010
English, Ru complexes with chiral diphosphines and amine-based ligands achieve high catalytic activity and enantioselectivity for the hydrogenation of ketones under neutral to slightly basic conditions. The chiral environment is controllable by changing the combination of these two ligands. A concerted six-membered transition state is proposed to be the origin of the high reactivity. The η6-arene/TsDPEN-Ru and MsDPEN-Cp*Ir catalysts effect the asymmetric reaction under slightly acidic conditions. A variety of chiral secondary alcohols are obtained in high enantiomeric excess. © 2010 The Japan Academy.

Asymmetric Cyanosilylation of alpha-Keto Esters Catalyzed by the [Ru(phgly)(2)(binap)]-C6H5OLi System
Nobuhito Kurono, Masato Uemura, Takeshi Ohkuma
EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2010, 8, 1455, 1459, WILEY-BLACKWELL, Mar. 2010
English, Scientific journal, The asymmetric reaction of alpha-keto esters and (CH3)(3)SiCN, catalyzed by a combined system of [Ru{(S)-phgly}(2){(S)-binap}] and C6H5OLi with a substrate-to-catalyst molar ratio (S/C) of 1000 at -60 degrees C, affords silylated cyanohydrins in up to 99 % ee. Cyanosilylation smoothly proceeds with an S/C of 10,000 at -50 degrees C. The use of Xyl-Binap instead of Binap as a ligand provides better enantioselectivity in some cases. A series of aromatic, hetero-aromatic, aliphatic, and alpha,beta-unsaturated keto esters are converted into the desired products.

Photosensitized intramolecular cyclization of furan and non-activated alkene: pathway switching by the substituent on the furan ring
Noriyoshi Arai, Koichiro Tanaka, Takeshi Ohkuma
TETRAHEDRON LETTERS, 51, 9, 1273, 1275, PERGAMON-ELSEVIER SCIENCE LTD, Mar. 2010
English, Scientific journal, A photosensitized reaction of furan with a non-activated simple alkene was investigated Intramolecular Diels-Alder-type cycloaddition reactions between furan and a trisubstituted alkene were found 10 proceed in high yield in the presence of 9,10-dicyanoanthracene under UV irradiation to afford oxabicyclo[2 2 1]heptane derivatives in high stereoselectivity when the furan was alkyl substituted. On the other hand, the aryl-substituted furan cyclized via a completely different pathway to give spirocyclic and tricyclic products. (C) 2009 Elsevier Ltd All rights reserved.

Asymmetric hydrogenation of ketones: Tactics to achieve high reactivity, enantioselectivity, and wide scope
Takeshi Ohkuma
PROCEEDINGS OF THE JAPAN ACADEMY SERIES B-PHYSICAL AND BIOLOGICAL SCIENCES, 86, 3, 202, 219, JAPAN ACAD, Mar. 2010, [Peer-reviewed]
English, Ru complexes with choral diphosphines and amine-based ligands achieve high catalytic activity and enantioselectivity for the hydrogenation of ketones under neutral to slightly basic conditions. The chiral environment is controllable by changing the combination of these two ligands. A concerted six-membered transition state is proposed to be the origin of the high reactivity. The eta(6)-arene/TsDPEN-Ru and MsDPEN Cp*Ir catalysts effect the asymmetric reaction under slightly acidic conditions. A. variety of chiral secondary alcohols are obtained ill high enantiomeric excess.

Chiral eta(6)-Arene/N-Tosylethylenediamine-Ruthenium(II) Complexes: Solution Behavior and Catalytic Activity for Asymmetric Hydrogenation
Christian A. Sandoval, Fusheng Bie, Aki Matsuoka, Yoshiki Yamaguchi, Hiroshi Naka, Yuehui Li, Koichi Kato, Noriyuki Utsumi, Kunihiko Tsutsumi, Takeshi Ohkuma, Kunihiko Murata, Ryoji Noyori
CHEMISTRY-AN ASIAN JOURNAL, 5, 4, 806, 816, WILEY-BLACKWELL, 2010
English, Scientific journal, Aromatic ketones are enantioseletively hydrogenated in alcohols containing [RuX{(S,S)-Tsdpen)(eta(6)-p-cymene)] (Tsdpen=TsNCH(C6H5)CH-(C6H3)NH2; X = TfO, Cl) as precatalysts. The corresponding Ru hydride (X = H) acts as a reducing species. The solution structures and complete spectral assignment of these complexes have been determined using 2D NMR (H-1-H-1 DQF-COSY, H-1-C-13 HMQC, HSQC, and H-1-F-19 HOESY). Depending on the nature of the solvents and conditions, the precatalysts exist as a covalently bound complex, tight ion pair of [Ru+(Tsdpen)(cymene)] and X-, solvent-separated ion pair, or discrete free ions. Solvent effects on the NH2 chemical shifts of the Ru complexes and the hydrodynamic radius and volume of the Re and TfO- ions elucidate the process of precatalyst activation for hydrogenation. Most notably, the Ru triflate possessing a high ionizability, substantiated by cyclic voltammetry, exists in alcoholic solvents largely as a solvent-separated ion pair and/or free ions. Accordingly, its diffusion-derived data in CD3OD reflect the independent motion of [Ru+(Tsdpen)(cymene) and TfO-. In CDCl3, the complex largely retains the covalent structure showing similar diffusion data for the cation and anion. The Ru triflate and chloride show similar but distinct solution behavior in various solvents. Conductivity measurements and catalytic behavior demonstrate that both complexes ionize in CH3OH to generate a common [Ru+(Tsdpen)(cymene)] and X-, although the extent is significantly greater for X = TfO-. The activation of [RuX(Tsdpen)(cymene)] during catalytic hydrogenation in alcoholic solvent occurs by simple ionization to generate [Ru+(Tsdpen)(cymene)]. The catalytic activity is thus significantly influenced by the reaction conditions.

ASYMMETRIC HYDROGENATION OF AROMATIC HETEROCYCLIC KETONES CATALYZED BY THE MsDPEN-Cp*Ir(III) COMPLEX
Noriyuki Utsumi, Kunihiko Tsutsumi, Masahiko Watanabe, Kunihiko Murata, Noriyoshi Arai, Nobuhito Kurono, Takeshi Ohkume
HETEROCYCLES, 80, 1, 141, 147, PERGAMON-ELSEVIER SCIENCE LTD, Jan. 2010
English, Scientific journal, Asymmetric hydrogenation of aromatic heterocyclic ketones catalyzed by Cp*Ir(OTf)(Msdpen) (MsDPEN = N-(methanesulfonyl)-1,2-diphenylethylenediamine) affords the heterocyclic alcohols in 93% to >99% ee. The reaction is conducted in a methanolic solution with a substrate-to-catalyst molar ratio of 200-5000 under 15 atm of H-2. The heterocyclic rings of substrates are left intact.

Chiral eta(6)-Arene/N-Tosylethylenediamine-Ruthenium(II) Complexes: Solution Behavior and Catalytic Activity for Asymmetric Hydrogenation
Christian A. Sandoval, Fusheng Bie, Aki Matsuoka, Yoshiki Yamaguchi, Hiroshi Naka, Yuehui Li, Koichi Kato, Noriyuki Utsumi, Kunihiko Tsutsumi, Takeshi Ohkuma, Kunihiko Murata, Ryoji Noyori
CHEMISTRY-AN ASIAN JOURNAL, 5, 4, 806, 816, WILEY-BLACKWELL, 2010, [Peer-reviewed]
English, Scientific journal, Aromatic ketones are enantioseletively hydrogenated in alcohols containing [RuX{(S,S)-Tsdpen)(eta(6)-p-cymene)] (Tsdpen=TsNCH(C6H5)CH-(C6H3)NH2; X = TfO, Cl) as precatalysts. The corresponding Ru hydride (X = H) acts as a reducing species. The solution structures and complete spectral assignment of these complexes have been determined using 2D NMR (H-1-H-1 DQF-COSY, H-1-C-13 HMQC, HSQC, and H-1-F-19 HOESY). Depending on the nature of the solvents and conditions, the precatalysts exist as a covalently bound complex, tight ion pair of [Ru+(Tsdpen)(cymene)] and X-, solvent-separated ion pair, or discrete free ions. Solvent effects on the NH2 chemical shifts of the Ru complexes and the hydrodynamic radius and volume of the Re and TfO- ions elucidate the process of precatalyst activation for hydrogenation. Most notably, the Ru triflate possessing a high ionizability, substantiated by cyclic voltammetry, exists in alcoholic solvents largely as a solvent-separated ion pair and/or free ions. Accordingly, its diffusion-derived data in CD3OD reflect the independent motion of [Ru+(Tsdpen)(cymene) and TfO-. In CDCl3, the complex largely retains the covalent structure showing similar diffusion data for the cation and anion. The Ru triflate and chloride show similar but distinct solution behavior in various solvents. Conductivity measurements and catalytic behavior demonstrate that both complexes ionize in CH3OH to generate a common [Ru+(Tsdpen)(cymene)] and X-, although the extent is significantly greater for X = TfO-. The activation of [RuX(Tsdpen)(cymene)] during catalytic hydrogenation in alcoholic solvent occurs by simple ionization to generate [Ru+(Tsdpen)(cymene)]. The catalytic activity is thus significantly influenced by the reaction conditions.

Asymmetric Hydrogenation of Ketones Catalyzed by Ru Complexes
OHKUMA TAKESHI
Catalysts & Catalysis, 51, 8, 577, 582, 触媒学会, 10 Dec. 2009, [Corresponding author]
Japanese, 10239699

Asymmetric Hydrogenation of Ketones Catalyzed by Ru Complexes.
OKUMA TAKESHI
触媒, 51, 8, 577-582, 582, 触媒学会, 10 Dec. 2009
Japanese

Highly Active and Selective Semihydrogenation of Alkynes with the Palladium Nanoparticles-Tetrabutylammonium Borohydride Catalyst System
Junichi Hori, Kunihiko Murata, Toshiki Sugai, Hisanori Shinohara, Ryoji Noyori, Noriyoshi Arai, Nobuhito Kurono, Takeshi Ohkuma
ADVANCED SYNTHESIS & CATALYSIS, 351, 18, 3143, 3149, WILEY-V C H VERLAG GMBH, Dec. 2009
English, Scientific journal, Palladium nanoparticles are prepared from palladium(II) acetate and 2 equivalents of potassium tert-butoxide in the presence of 4-octyne. The palladium nanoparticles-tetrabutylammonium borohydride system shows excellent catalytic activity and selectivity in the semihydrogenation of alkynes to the [ (Z)-]alkenes. The hydrogenation of 4-octyne is conducted with the catalyst system at a substrate-to-palladium molar ratio of 10,000-200,000 under 8 atm of hydrogen to give (Z)-4-octene in > 99% yield. Isomerization and over-reduction of the Z-alkene are very slow even after consumption of the alkyne.

BINAP/DMAPEN—Ru(II)錯体触媒を用いるカルコン類の不斉水素化反応
新井則義, 東慶太, 新居紀之, 大熊毅
万有生命科学振興国際交流財団札幌シンポジウム, 21st, 45, 04 Jul. 2009
Japanese

銅触媒によるラセミ体α‐ヒドロキシエステル類の速度論分割の研究
黒野暢仁, 大津賀健太郎, 若林真徳, 近藤忠弘, 大岡浩仁, 大熊毅
日本化学会北海道支部夏季研究発表会講演要旨集, 2009, 8, 26 Jun. 2009
Japanese

フランと単純アルケンとの光増感Diels‐Alder反応の開発研究
新井則義, 田中皓一朗, 大熊毅
日本化学会北海道支部夏季研究発表会講演要旨集, 2009, 20, 26 Jun. 2009
Japanese

ルテニウム錯体を用いるアルデヒド類の不斉シアノシリル化反応
植村真人, 新井健太, 黒野暢仁, 大熊毅
万有生命科学振興国際交流財団福岡シンポジウム, 19th, 40, 23 May 2009
Japanese

Practical Asymmetric Hydrogenation of 3-Quinuclidinone Catalyzed by the XylSkewphos/PICA-Ruthenium(II) Complex
Kunihiko Tsutsumi, Takeaki Katayama, Noriyuki Utsumi, Kunihiko Murata, Noriyoshi Arai, Nobuhito Kurono, Takeshi Ohkuma
ORGANIC PROCESS RESEARCH & DEVELOPMENT, 13, 3, 625, 628, AMER CHEMICAL SOC, May 2009
English, Asymmetric hydrogenation of 3-quinuclidinone with RuBr(2)[ (S,S)-xylskewphos](pica) in a base containing ethanol affords (R)-3-quinuclidinol in 88-90% ee (XylSkewphos = 2,4-bis(di-3,5-xylylphosphino)pentane, PICA = alpha-picolylamine). The optical purity of the product is readily increased to >99% by recrystallization. The hydrogenation of a 4.3-kg scale with a substrate-to-catalyst molar ratio of 100 000 under 15 atm of H(2) at 30-45 degrees C completes in 4 h. Use of methanol or 2-propanol as a solvent decreases the catalyst efficiency. RuCl(2)(skewphos)(pica), and RuCl(2)(tolbinap)(pica) which have similar structures, are less effective for this reaction.

不飽和化合物の不斉還元—目的に応じた反応と試薬の選び方—
大熊毅
有機合成化学講習会テキスト, 2009, 61-71, 2009
Japanese

Asymmetric Hydrogenation of Aromatic Ketones Catalyzed by the TolBINAP/DMAPEN-Ruthenium(II) Complex: A Significant Effect of N-Substituents of Chiral 1,2-Diamine Ligands on Enantioselectivity
Hirohito Ooka, Noriyoshi Arai, Keita Azuma, Nobuhito Kurono, Takeshi Ohkuma
JOURNAL OF ORGANIC CHEMISTRY, 73, 22, 9084, 9093, AMER CHEMICAL SOC, Nov. 2008
English, Scientific journal, Asymmetric hydrogenation of acetophenone in the presence of Ru(II) catalysts coordinated by TolBINAP and a series of chiral 1,2-diamines was studied. The sense and degree of enantioselectivity were highly dependent on the N-substituents of the diamine ligands. The N-substituent effect was discussed in detail. Among these catalysts, the (S)-TolBINAP/(R)DMAPEN-Ru(II) complex showed the highest enantioselectivity. The mode of enantioface selection was interpreted by using transition state models based on the X-ray structure of the catalyst precursor. The chiral catalyst effected the hydrogenation of alkyl aryl ketones and arylglyoxal dialkyl acetals to afford the chiral alcohol in >99% ee in the best cases. Hydrogenation of racemic benzoin methyl ether with the chiral catalyst through dynamic kinetic resolution gave the anti-alcohol (syn:anti = 3:97) in 98% ee, while the reaction of alpha-amidopropiophenones resulted in the syn-alcohols (syn:anti = 96:4 to >99:1) in >98% ee.

Asymmetric Hydrogenation of Aromatic Ketones Catalyzed by the TolBINAP/DMAPEN-Ruthenium(II) Complex: A Significant Effect of N-Substituents of Chiral 1,2-Diamine Ligands on Enantioselectivity
Hirohito Ooka, Noriyoshi Arai, Keita Azuma, Nobuhito Kurono, Takeshi Ohkuma
JOURNAL OF ORGANIC CHEMISTRY, 73, 22, 9084, 9093, AMER CHEMICAL SOC, Nov. 2008, [Peer-reviewed]
English, Scientific journal, Asymmetric hydrogenation of acetophenone in the presence of Ru(II) catalysts coordinated by TolBINAP and a series of chiral 1,2-diamines was studied. The sense and degree of enantioselectivity were highly dependent on the N-substituents of the diamine ligands. The N-substituent effect was discussed in detail. Among these catalysts, the (S)-TolBINAP/(R)DMAPEN-Ru(II) complex showed the highest enantioselectivity. The mode of enantioface selection was interpreted by using transition state models based on the X-ray structure of the catalyst precursor. The chiral catalyst effected the hydrogenation of alkyl aryl ketones and arylglyoxal dialkyl acetals to afford the chiral alcohol in >99% ee in the best cases. Hydrogenation of racemic benzoin methyl ether with the chiral catalyst through dynamic kinetic resolution gave the anti-alcohol (syn:anti = 3:97) in 98% ee, while the reaction of alpha-amidopropiophenones resulted in the syn-alcohols (syn:anti = 96:4 to >99:1) in >98% ee.

銅触媒によるα‐ヒドロキシラクトン類のエナンチオマー選択的カーバメート化反応
若林真徳, 近藤忠弘, 大岡浩仁, 田地川浩人, 黒野暢仁, 大熊毅
日本化学会北海道支部研究発表会講演要旨集, 2008, 34, 19 Jul. 2008
Japanese

ルテニウム錯体を用いるアルデヒド類の不斉シアノシリル化反応
植村真人, 新井健太, 黒野暢仁, 大熊毅
日本化学会北海道支部研究発表会講演要旨集, 2008, 33, 19 Jul. 2008
Japanese

ルテニウム錯体を用いるアルデヒド類の不斉シアノシリル化反応
植村真人, 新井健太, 黒野暢仁, 大熊毅
万有生命科学振興国際交流財団札幌シンポジウム, 20th, 56, 05 Jul. 2008
Japanese

Carbonyl Hydroboration
Noriyoshi Arai, Takeshi Ohkuma
Modern Reduction Methods, 159, 181, John Wiley and Sons, 04 Apr. 2008, [Peer-reviewed]
English, In book

MsDPEN‐Cp^*イリジウム錯体触媒を用いるα‐ヒドロキシケトン類の不斉水素化反応
大熊毅, 内海典之, 渡辺正人, 堤邦彦, 新井則義, 村田邦彦
日本化学会講演予稿集, 88th, 2, 1158, 12 Mar. 2008
Japanese

銅触媒によるラセミ体α‐ヒドロキシエステル類の速度論分割の研究
近藤忠弘, 大岡浩仁, 黒野暢仁, 大熊毅
日本化学会講演予稿集, 88th, 2, 1269, 12 Mar. 2008
Japanese

ルテニウム錯体を用いるアルデヒド類の不斉シアノシリル化反応
黒野暢仁, 新井健太, 植村真人, 大熊毅
日本化学会講演予稿集, 88th, 2, 1264, 12 Mar. 2008
Japanese

TolBINAP/ジアミン‐ルテニウム(II)錯体を用いるアシルシラン類の触媒的不斉水素化反応
新井則義, 鈴木賢, 杉崎聡, 反町尋子, 大熊毅
日本化学会講演予稿集, 88th, 2, 1108, 12 Mar. 2008
Japanese

TolBINAP/ジアミン‐ルテニウム(II)錯体を用いるカルコン類の触媒的不斉水素化
新井則義, 東慶太, 新居紀之, 大熊毅
日本化学会講演予稿集, 88th, 2, 1107, 12 Mar. 2008
Japanese

銅触媒によるα‐ヒドロキシラクトン類のエナンチオマー選択的カーバメート化反応
若林真徳, 近藤忠弘, 大岡浩仁, 田地川浩人, 黒野暢仁, 大熊毅
日本化学会講演予稿集, 88th, 2, 1268, 12 Mar. 2008
Japanese

Enantioselective Ketone and β-Keto Ester Hydrogenations (Including Mechanisms)
Takeshi Ohkuma, Ryoji Noyori
The Handbook of Homogeneous Hydrogenation, 1105, 1163, John Wiley and Sons, 31 Jan. 2008, [Peer-reviewed]
English, In book

Highly enantioselective hydrogenation of aryl vinyl ketones to allylic alcohols catalyzed by the tol-binap/dmapen ruthenium(II) complex
Noriyoshi Arai, Keita Azuma, Noriyuki Nii, Takeshi Ohkuma
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 47, 39, 7457, 7460, WILEY-BLACKWELL, 2008
English, Scientific journal

[Ru(phgly)(2)(binap)]/Li(2)CO(3): A highly active, robust, and enantioselective catalyst for the cyanosilylation of aldehydes
Nobuhito Kurono, Kenta Arai, Masato Uemura, Takeshi Ohkuma
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 47, 35, 6643, 6646, WILEY-BLACKWELL, 2008
English, Scientific journal

Enantiomer-selective carbamoylation of racemic alpha-hydroxy gamma-lactones with chiral Cu-II catalysts: An example of a highly active Lewis acid catalyzed reaction
Nobuhito Kurono, Tadahiro Kondo, Masanori Wakabayashi, Hirohito Ooka, Tsutomu Inoue, Hiroto Tachikawa, Takeshi Ohkuma
CHEMISTRY-AN ASIAN JOURNAL, 3, 8-9, 1289, 1297, WILEY-V C H VERLAG GMBH, 2008
English, Scientific journal, Enantiomer-selective carbamoylation of racemic alpha-hydroxy gamma-lactones with half equivalents of isocyanates in the presence of chiral Cu-II catalysts was studied. Among a series of catalyst bearing chiral bis(oxazoline) (box) and pyridine(bisoxazoline) ligands, [Cu(tBu-box)]X-2 [X=OSO2CF3 (3a), SbF6 (3b)] showed the highest enantioselectivity in the reaction of pantolactone (1a). Use of n-C3H7NCO, a small alkyl isocyanate, in CH2Cl2 solution was important to achieve a high level of enantiomer selection. The tBu-box-Cu-II catalyst efficiently differentiated two enantiomers of beta-substituted alpha-hydroxy gamma-lactones under the optimized reaction conditions, resulting in a stereoselectivity factor (s = k(fast)/k(slow)) of up to 209. Furthermore, this catalyst is highly active, so that the carbamoylation can be conducted with a substrate-to-catalyst molar ratio of 2000-3000. A catalytic cycle of this reaction is also proposed.

Asymmetric hydrogenation of aromatic, aliphatic, and alpha,beta-unsaturated acyl silanes catalyzed by tol-binap/pica ruthenium(II) complexes: Practical synthesis of optically active alpha-hydroxysilanes
Noriyoshi Arai, Ken Suzuki, Satoshi Sugizaki, Hiroko Sorimachi, Takeshi Ohkuma
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 47, 9, 1770, 1773, WILEY-BLACKWELL, 2008
English, Scientific journal

TolBINAP/ジアミン‐ルテニウム(II)錯体を用いるカルコン類の触媒的不斉水素化
新井則義, 東慶太, 新居紀之, 大熊毅
有機合成シンポジウム講演要旨集, 94th, 98-99, 2008
Japanese

分子集合体型錯体触媒を用いるケトン類およびイミン類の不斉水素化 平成18‐19年度
大熊毅
分子集合体型錯体触媒を用いるケトン類およびイミン類の不斉水素化 平成18−19年度 No.18350046, 241P, 2008
Japanese

Asymmetric hydrogenation of aromatic, aliphatic, and alpha,beta-unsaturated acyl silanes catalyzed by tol-binap/pica ruthenium(II) complexes: Practical synthesis of optically active alpha-hydroxysilanes
Noriyoshi Arai, Ken Suzuki, Satoshi Sugizaki, Hiroko Sorimachi, Takeshi Ohkuma
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 47, 9, 1770, 1773, WILEY-BLACKWELL, 2008, [Peer-reviewed]
English, Scientific journal

Enantiomer-selective carbamoylation of racemic alpha-hydroxy gamma-lactones with chiral Cu-II catalysts: An example of a highly active Lewis acid catalyzed reaction
Nobuhito Kurono, Tadahiro Kondo, Masanori Wakabayashi, Hirohito Ooka, Tsutomu Inoue, Hiroto Tachikawa, Takeshi Ohkuma
CHEMISTRY-AN ASIAN JOURNAL, 3, 8-9, 1289, 1297, WILEY-V C H VERLAG GMBH, 2008, [Peer-reviewed]
English, Scientific journal, Enantiomer-selective carbamoylation of racemic alpha-hydroxy gamma-lactones with half equivalents of isocyanates in the presence of chiral Cu-II catalysts was studied. Among a series of catalyst bearing chiral bis(oxazoline) (box) and pyridine(bisoxazoline) ligands, [Cu(tBu-box)]X-2 [X=OSO2CF3 (3a), SbF6 (3b)] showed the highest enantioselectivity in the reaction of pantolactone (1a). Use of n-C3H7NCO, a small alkyl isocyanate, in CH2Cl2 solution was important to achieve a high level of enantiomer selection. The tBu-box-Cu-II catalyst efficiently differentiated two enantiomers of beta-substituted alpha-hydroxy gamma-lactones under the optimized reaction conditions, resulting in a stereoselectivity factor (s = k(fast)/k(slow)) of up to 209. Furthermore, this catalyst is highly active, so that the carbamoylation can be conducted with a substrate-to-catalyst molar ratio of 2000-3000. A catalytic cycle of this reaction is also proposed.

[Ru(phgly)(2)(binap)]/Li(2)CO(3): A highly active, robust, and enantioselective catalyst for the cyanosilylation of aldehydes
Nobuhito Kurono, Kenta Arai, Masato Uemura, Takeshi Ohkuma
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 47, 35, 6643, 6646, WILEY-BLACKWELL, 2008, [Peer-reviewed]
English, Scientific journal

Highly enantioselective hydrogenation of aryl vinyl ketones to allylic alcohols catalyzed by the tol-binap/dmapen ruthenium(II) complex
Noriyoshi Arai, Keita Azuma, Noriyuki Nii, Takeshi Ohkuma
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 47, 39, 7457, 7460, WILEY-BLACKWELL, 2008, [Peer-reviewed]
English, Scientific journal

Tailor-made catalysts for asymmetric hydrogenation of ketones
Takeshi Ohkuma
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN, 65, 11, 1070, 1080, SOC SYNTHETIC ORGANIC CHEM JPN, Nov. 2007
English, Scientific journal, Asymmetric hydrogenation of ketones catalyzed by XylBINAP/chiral diamine-Ru(II), TolBINAP/PICA-Ru(II), eta(6)-arene/TsDPEN-Ru(II), and MsDPEN-Cp*lr(III) complexes affords a variety of secondary alcohols with high enantioselectivity. Complete conversion is attainable with a low catalyst loading. The high catalyst efficiency is rationalized by a novel "metal-ligand cooperative mechanism."

On the synthesis of protopine alkaloids
Yasuhiro Wada, Harumi Kaga, Shiho Uchiito, Eri Kumazawa, Miho Tomiki, Yu Onozaki, Nobuhito Kurono, Masao Tokuda, Takeshi Ohkuma, Kazuhiko Orito
JOURNAL OF ORGANIC CHEMISTRY, 72, 19, 7301, 7306, AMER CHEMICAL SOC, Sep. 2007
English, Scientific journal, [GRAPHICS]
For the synthesis of protopine alkaloids, we studied a reaction sequence based on a ring enlargement of indeno[2,1-a][3]benzazepines by a singlet oxygen oxygenation, followed by conversion of an amide carbonyl group of the resultant 10-membered keto-lactam to a methylene group, which is the last step for completion of the synthesis. The key substances, indeno[2,1-a][3]benzazepines, were prepared by Bischler-Napieralski cyclization of alkoxy-substituted 1-(2-bromobenzyl)-3-benzazepin-2-ones. Steric effects of the substituents in this synthesis were examined.

On the synthesis of protopine alkaloids
Yasuhiro Wada, Harumi Kaga, Shiho Uchiito, Eri Kumazawa, Miho Tomiki, Yu Onozaki, Nobuhito Kurono, Masao Tokuda, Takeshi Ohkuma, Kazuhiko Orito
JOURNAL OF ORGANIC CHEMISTRY, 72, 19, 7301, 7306, AMER CHEMICAL SOC, Sep. 2007, [Peer-reviewed]
English, Scientific journal, [GRAPHICS]
For the synthesis of protopine alkaloids, we studied a reaction sequence based on a ring enlargement of indeno[2,1-a][3]benzazepines by a singlet oxygen oxygenation, followed by conversion of an amide carbonyl group of the resultant 10-membered keto-lactam to a methylene group, which is the last step for completion of the synthesis. The key substances, indeno[2,1-a][3]benzazepines, were prepared by Bischler-Napieralski cyclization of alkoxy-substituted 1-(2-bromobenzyl)-3-benzazepin-2-ones. Steric effects of the substituents in this synthesis were examined.

α位分枝芳香族ケトン類の不斉水素化
新井則義, 大岡浩仁, 大岡浩仁, 東慶太, 薮内俊夫, 井上勉, 大熊毅
万有生命科学振興国際交流財団札幌シンポジウム, 19th, 38, 07 Jul. 2007
Japanese

Asymmetric hydrogenation of alpha-hydroxy ketones catalyzed by MsDPEN-Cp*Ir(III) complex
Takeshi Ohkuma, Noriyuki Utsumi, Masahito Watanabe, Kunihiko Tsutsumi, Noriyoshi Arai, Kunihiko Murata
ORGANIC LETTERS, 9, 13, 2565, 2567, AMER CHEMICAL SOC, Jun. 2007
English, Scientific journal, Asymmetric hydrogenation of a series of alpha-hydroxy aromatic ketones in methanol catalyzed by Cp*Ir(OTf)(MsDPEN) (MsDPEN = N-(methanesulfonyl)-1,2-diphenylethylenediamine) affords the 1-aryl-1,2-ethanediols in up to 99% ee. The reaction can be conducted with a substrate-to-catalyst molar ratio as high as 6000 under 10 atm of H-2. 1-Hydroxy-2-propanone is also hydrogenated with high enantioselectivity.

水素結合を活用したキラル有機触媒
黒野暢仁, 大熊毅
化学, 62, 6, 66-67, 01 Jun. 2007
Japanese

Asymmetric hydrogenation of alpha-hydroxy ketones catalyzed by MsDPEN-Cp*Ir(III) complex
Takeshi Ohkuma, Noriyuki Utsumi, Masahito Watanabe, Kunihiko Tsutsumi, Noriyoshi Arai, Kunihiko Murata
ORGANIC LETTERS, 9, 13, 2565, 2567, AMER CHEMICAL SOC, Jun. 2007, [Peer-reviewed]
English, Scientific journal, Asymmetric hydrogenation of a series of alpha-hydroxy aromatic ketones in methanol catalyzed by Cp*Ir(OTf)(MsDPEN) (MsDPEN = N-(methanesulfonyl)-1,2-diphenylethylenediamine) affords the 1-aryl-1,2-ethanediols in up to 99% ee. The reaction can be conducted with a substrate-to-catalyst molar ratio as high as 6000 under 10 atm of H-2. 1-Hydroxy-2-propanone is also hydrogenated with high enantioselectivity.

α位分枝芳香族ケトン類の不斉水素化
新井則義, 大岡浩仁, 東慶太, 薮内俊夫, 井上勉, 大熊毅
日本化学会講演予稿集, 87th, 2, 1002, 12 Mar. 2007
Japanese

光学活性ルテニウム錯体触媒によるα‐クロロアセトフェノン類の不斉水素化反応
堤邦彦, 大熊毅, 内海典之, 新井則義, 野依良治, 村田邦彦
日本化学会講演予稿集, 87th, 2, 1002, 12 Mar. 2007
Japanese

η⁶‐アレーン/TsDPEN‐ルテニウム錯体触媒を用いるケトン類の不斉水素化:光学活性4‐クロマノールの合成
内海典之, 大熊毅, 堤邦彦, 村田邦彦, SANDOVAL C. A, 野依良治, 野依良治
日本化学会講演予稿集, 87th, 2, 1002, 12 Mar. 2007
Japanese

General asymmetric hydrogenation of alpha-branched aromatic ketones catalyzed by TolBINAP/DMAPEN-ruthenium(II) complex
Noriyoshi Arai, Hirohito Ooka, Keita Azuma, Toshio Yabuuchi, Nobuhito Kurono, Tsutomu Inoue, Takeshi Ohkuma
ORGANIC LETTERS, 9, 5, 939, 941, AMER CHEMICAL SOC, Mar. 2007
English, Scientific journal, A catalyst system consisting of RuCl2[ (S)-tolbinap][ (R)-dmapen] and t-C4H9OK in 2-propanol effects asymmetric hydrogenation of arylglyoxal dialkylacetals to give the alpha-hydroxy acetals in up to 98% ee. Hydrogenation of racemic alpha-amidopropiophenones under dynamic kinetic resolution predominantly gives the syn alcohols in up to 99% ee and > 98% de, while the reaction of racemic bezoin methyl ether gives the anti alcohols in excellent stereoselectivity.

General asymmetric hydrogenation of alpha-branched aromatic ketones catalyzed by TolBINAP/DMAPEN-ruthenium(II) complex
Noriyoshi Arai, Hirohito Ooka, Keita Azuma, Toshio Yabuuchi, Nobuhito Kurono, Tsutomu Inoue, Takeshi Ohkuma
ORGANIC LETTERS, 9, 5, 939, 941, AMER CHEMICAL SOC, Mar. 2007, [Peer-reviewed]
English, Scientific journal, A catalyst system consisting of RuCl2[ (S)-tolbinap][ (R)-dmapen] and t-C4H9OK in 2-propanol effects asymmetric hydrogenation of arylglyoxal dialkylacetals to give the alpha-hydroxy acetals in up to 98% ee. Hydrogenation of racemic alpha-amidopropiophenones under dynamic kinetic resolution predominantly gives the syn alcohols in up to 99% ee and > 98% de, while the reaction of racemic bezoin methyl ether gives the anti alcohols in excellent stereoselectivity.

Asymmetric hydrogenation of alpha-chloro aromatic ketones catalyzed by eta(6)-arene/TsDPEN-ruthenium(II) complexes
Takeshi Ohkuma, Kunihiko Tsutsumi, Noriyuki Utsumi, Noriyoshi Arai, Ryoji Noyori, Kunihiko Murata
ORGANIC LETTERS, 9, 2, 255, 257, AMER CHEMICAL SOC, Jan. 2007
English, Scientific journal, Asymmetric hydrogenation of various alpha-chloro aromatic ketones with Ru(OTf)(TsDPEN)(eta(6)-arene) (TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine) produces the chiral chlorohydrins in up to 98% ee. This reaction can be conducted even on a 206-g scale. The hydrogenation of an alpha-chloro ketone with a phenol moiety has been utilized for the synthesis of (R)-norphenylephrine without protection-deprotection operations.

Synthesis of a 3-arylisoquinoline alkaloid, decumbenine B
Yasuhiro Wada, Naoto Nishida, Nobuhito Kurono, Takashi Ohkuma, Kazuhiko Orito
European Journal of Organic Chemistry, 2007, 26, 4320, 4327, 2007
English, Scientific journal, The synthesis of a 3-arylisoquinoline alkaloid, decumbenine B, was accomplished in a reaction sequence based on the formation of an indolizine ring (dibenz[a,f]indolizin-5(7H)-one) followed by its cleavage at the amide bond, starting with an interaction of 5,6-(methylenedioxy)isoquinoline with 2-bromo-5,6-(methylenedioxy)benzoyl chloride in the presence of Bu 3SnH. © Wiley-VCH Verlag GmbH &
Co. KGaA, 2007.

Asymmetric hydrogenation of alpha-chloro aromatic ketones catalyzed by eta(6)-arene/TsDPEN-ruthenium(II) complexes
Takeshi Ohkuma, Kunihiko Tsutsumi, Noriyuki Utsumi, Noriyoshi Arai, Ryoji Noyori, Kunihiko Murata
ORGANIC LETTERS, 9, 2, 255, 257, AMER CHEMICAL SOC, Jan. 2007, [Peer-reviewed]
English, Scientific journal, Asymmetric hydrogenation of various alpha-chloro aromatic ketones with Ru(OTf)(TsDPEN)(eta(6)-arene) (TsDPEN = N-(p-toluenesulfonyl)-1,2-diphenylethylenediamine) produces the chiral chlorohydrins in up to 98% ee. This reaction can be conducted even on a 206-g scale. The hydrogenation of an alpha-chloro ketone with a phenol moiety has been utilized for the synthesis of (R)-norphenylephrine without protection-deprotection operations.

The hydrogenation/transfer hydrogenation network: Asymmetric hydrogenation of ketones with chiral eta(6)-arene/N-tosylethylenediamine-ruthenium(II) catalysts
Takeshi Ohkuma, Noriyuki Utsumi, Kunihiko Tsutsumi, Kunihiko Murata, Christian Sandoval, Ryoji Noyori
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 128, 27, 8724, 8725, AMER CHEMICAL SOC, Jul. 2006
English, Scientific journal

Mechanism of asymmetric hydrogenation of acetophenone catalyzed by chiral eta(6)-arene-N-tosylethylenediamine-ruthenium(II) complexes
Christian A. Sandoval, Takeshi Ohkuma, Noriyuki Utsumi, Kunihiko Tsutsumi, Kunihiko Murata, Ryoji Noyori
CHEMISTRY-AN ASIAN JOURNAL, 1, 1-2, 102, 110, WILEY-V C H VERLAG GMBH, Jul. 2006
English, Scientific journal, Chiral arene-N-tosylethylenediamine-Ru-II complexes can be made to effect both asymmetric transfer hydrogenation and asymmetric hydrogenation of simple ketones through a slight functional modification and by switching reaction conditions. [Ru(OSO2CF3){S,S)-TsNCH(C6H5)CH(C6H5)NH2)(eta(6) -p-cymene)] catalyzes the asymmetric hydrogenation of acetophenone in methanol to afford (S)-1-phenylethanol with 96% ee in 100% yield. Like the transfer hydrogenation catalyzed by similar Ru catalysts with basic 2-propanol or a formic acid/triethylamine mixture, this hydrogenation proceeds through a metal-ligand bifunctional mechanism. The reduction of the C=O function occurs via an intermediary18e RuH species in its outer coordination sphere without metal-substrate interaction. The high catalytic efficiency relies on the facile ionization of the Ru triflate complex in methanol. The turnover rate is dependent on hydrogen pressure and medium acidity and basicity. The RuCl analogue can be used as a precatalyst, albeit less effectively. Unlike the well-known diphosphine-1,2-diamine-Ru-II-catalyzed hydrogenation that proceeds in a basic alcohol, this reaction takes place under slightly acidic conditions, creating new opportunities for asymmetric hydrogenation.

The hydrogenation/transfer hydrogenation network: Asymmetric hydrogenation of ketones with chiral eta(6)-arene/N-tosylethylenediamine-ruthenium(II) catalysts
Takeshi Ohkuma, Noriyuki Utsumi, Kunihiko Tsutsumi, Kunihiko Murata, Christian Sandoval, Ryoji Noyori
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 128, 27, 8724, 8725, AMER CHEMICAL SOC, Jul. 2006, [Peer-reviewed]
English, Scientific journal

Mechanism of asymmetric hydrogenation of acetophenone catalyzed by chiral eta(6)-arene-N-tosylethylenediamine-ruthenium(II) complexes
Christian A. Sandoval, Takeshi Ohkuma, Noriyuki Utsumi, Kunihiko Tsutsumi, Kunihiko Murata, Ryoji Noyori
CHEMISTRY-AN ASIAN JOURNAL, 1, 1-2, 102, 110, WILEY-V C H VERLAG GMBH, Jul. 2006, [Peer-reviewed]
English, Scientific journal, Chiral arene-N-tosylethylenediamine-Ru-II complexes can be made to effect both asymmetric transfer hydrogenation and asymmetric hydrogenation of simple ketones through a slight functional modification and by switching reaction conditions. [Ru(OSO2CF3){S,S)-TsNCH(C6H5)CH(C6H5)NH2)(eta(6) -p-cymene)] catalyzes the asymmetric hydrogenation of acetophenone in methanol to afford (S)-1-phenylethanol with 96% ee in 100% yield. Like the transfer hydrogenation catalyzed by similar Ru catalysts with basic 2-propanol or a formic acid/triethylamine mixture, this hydrogenation proceeds through a metal-ligand bifunctional mechanism. The reduction of the C=O function occurs via an intermediary18e RuH species in its outer coordination sphere without metal-substrate interaction. The high catalytic efficiency relies on the facile ionization of the Ru triflate complex in methanol. The turnover rate is dependent on hydrogen pressure and medium acidity and basicity. The RuCl analogue can be used as a precatalyst, albeit less effectively. Unlike the well-known diphosphine-1,2-diamine-Ru-II-catalyzed hydrogenation that proceeds in a basic alcohol, this reaction takes place under slightly acidic conditions, creating new opportunities for asymmetric hydrogenation.

Ligand Design for Catalytic Asymmetric Reduction
Takeshi Ohkuma, Masato Kitamura, Ryoji Noyori
New Frontiers in Asymmetric Catalysis, 1, 32, John Wiley & Sons, Inc., 14 Jun. 2006, [Peer-reviewed]
English, In book

Cyanosilylation of hetero-substituted ketones catalyzed by LiCl
N Kurono, K Suzuki, T Ohkuma
LETTERS IN ORGANIC CHEMISTRY, 3, 4, 275, 277, BENTHAM SCIENCE PUBL LTD, Apr. 2006
English, Scientific journal, LiCl efficiently catalyzes cyanosilylation of various hetero-substituted ketones. alpha,alpha-Dialkoxy ketones are completely converted to silylated cyanohydrins with a substrate-to-catalyst molar ratio of 100,000 at room temperature. Acctophenones substituted by an electron-attracting group at the ortho or para position show higher reactivity than substrates with an electron-donating function.

Solution structures and behavior of trans-RuH(eta(1)-BH4) (binap)(1,2-diamine) complexes
CA Sandoval, Y Yamaguchi, T Ohkuma, K Kato, R Noyori
MAGNETIC RESONANCE IN CHEMISTRY, 44, 1, 66, 75, JOHN WILEY & SONS LTD, Jan. 2006
English, Scientific journal, The solution structures of a number of trans-RuH(eta(1)-BH4)[ (S)-tolbinap](1,2-diamine) precatalysts [Tol-BINAP = 2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl; 1,2-diamine=(S,S)- or (RR)-1,2-diphenylethylene-diamine (DPEN), ethylenediamine (EN), and (S)-1,1-di(4-anisyl)-2-isopropylethylenediamine (DAIPEN)] have been determined using 2D NMR (H-1-H-1 DQF-COSY, H-1-C-13 HMQC, H-1-P-31 HSQC, and H-1-N-15 HSQC), and a double-pulsed field-gradient spin-echo (DPFGSE) NOE technique. All the octahedral Ru complexes adopt a trans configuration with respect to the BH4 and hydride ligands. Amine protons of trans-RuH(eta(1)-BH4)[ (S)-tolbinap](1,2-diamine) complexes undergo H/D exchange in (CD3)(2)CDOD. This inherent high acidity, coupled with the lability and chemical properties of the BH4 ligand, allows for precatalyst activation without the need for an added base, in contrast to trans-RuCl2[ (S)-tolbinapj(1,2diamine) precatalysts, which require a strong base for generation of a catalytic species. The H/BH4 complex in a 2-propanol solution is converted to catalytically active [trans-RuH((S)-tolbinap)((S,S)-dpen}(ROH)(+) [ (RO)(ROH)(n)](-) (R = (CH3)(2)CH), a loosely associated ion pair of the discrete (solvated) cationic fragment and anionic species. Copyright (c) 2006 John Wiley & Sons, Ltd.

Solution structures and behavior of trans-RuH(eta(1)-BH4) (binap)(1,2-diamine) complexes
CA Sandoval, Y Yamaguchi, T Ohkuma, K Kato, R Noyori
MAGNETIC RESONANCE IN CHEMISTRY, 44, 1, 66, 75, JOHN WILEY & SONS LTD, Jan. 2006, [Peer-reviewed]
English, Scientific journal, The solution structures of a number of trans-RuH(eta(1)-BH4)[ (S)-tolbinap](1,2-diamine) precatalysts [Tol-BINAP = 2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl; 1,2-diamine=(S,S)- or (RR)-1,2-diphenylethylene-diamine (DPEN), ethylenediamine (EN), and (S)-1,1-di(4-anisyl)-2-isopropylethylenediamine (DAIPEN)] have been determined using 2D NMR (H-1-H-1 DQF-COSY, H-1-C-13 HMQC, H-1-P-31 HSQC, and H-1-N-15 HSQC), and a double-pulsed field-gradient spin-echo (DPFGSE) NOE technique. All the octahedral Ru complexes adopt a trans configuration with respect to the BH4 and hydride ligands. Amine protons of trans-RuH(eta(1)-BH4)[ (S)-tolbinap](1,2-diamine) complexes undergo H/D exchange in (CD3)(2)CDOD. This inherent high acidity, coupled with the lability and chemical properties of the BH4 ligand, allows for precatalyst activation without the need for an added base, in contrast to trans-RuCl2[ (S)-tolbinapj(1,2diamine) precatalysts, which require a strong base for generation of a catalytic species. The H/BH4 complex in a 2-propanol solution is converted to catalytically active [trans-RuH((S)-tolbinap)((S,S)-dpen}(ROH)(+) [ (RO)(ROH)(n)](-) (R = (CH3)(2)CH), a loosely associated ion pair of the discrete (solvated) cationic fragment and anionic species. Copyright (c) 2006 John Wiley & Sons, Ltd.

Lithium chloride: An active and simple catalyst for cyanosilylation of aldehydes and ketones
N Kurono, M Yamaguchi, K Suzuki, T Ohkuma
JOURNAL OF ORGANIC CHEMISTRY, 70, 16, 6530, 6532, AMER CHEMICAL SOC, Aug. 2005
English, Scientific journal, LiCl acts as a highly effective catalyst for cyanosilylation of various aldehydes and ketones to the corresponding silylated cyanohydrins. The reaction proceeds smoothly with a substrate/catalyst molar ratio of 100-100 000 at 20-25 degrees C under solvent-free conditions. alpha,beta-Unsaturated aldehydes are completely converted to the 1,2-adducts. The cyanation products can be isolated by direct distillation of the reaction mixture.

Lithium chloride: An active and simple catalyst for cyanosilylation of aldehydes and ketones
N Kurono, M Yamaguchi, K Suzuki, T Ohkuma
JOURNAL OF ORGANIC CHEMISTRY, 70, 16, 6530, 6532, AMER CHEMICAL SOC, Aug. 2005, [Peer-reviewed]
English, Scientific journal, LiCl acts as a highly effective catalyst for cyanosilylation of various aldehydes and ketones to the corresponding silylated cyanohydrins. The reaction proceeds smoothly with a substrate/catalyst molar ratio of 100-100 000 at 20-25 degrees C under solvent-free conditions. alpha,beta-Unsaturated aldehydes are completely converted to the 1,2-adducts. The cyanation products can be isolated by direct distillation of the reaction mixture.

Asymmetric hydrogenation of tert-alkyl ketones
T Ohkuma, CA Sandoval, R Srinivasan, Q Lin, Y Wei, K Muniz, R Noyori
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 127, 23, 8288, 8289, AMER CHEMICAL SOC, Jun. 2005
English, Scientific journal

Asymmetric hydrogenation of tert-alkyl ketones
T Ohkuma, CA Sandoval, R Srinivasan, Q Lin, Y Wei, K Muniz, R Noyori
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 127, 23, 8288, 8289, AMER CHEMICAL SOC, Jun. 2005, [Peer-reviewed]
English, Scientific journal

Metal-ligand bifunctional catalysis for asymmetric hydrogenation
R Noyori, CA Sandoval, K Muniz, T Ohkuma
PHILOSOPHICAL TRANSACTIONS OF THE ROYAL SOCIETY A-MATHEMATICAL PHYSICAL AND ENGINEERING SCIENCES, 363, 1829, 901, 912, ROYAL SOCIETY, Apr. 2005
English, Scientific journal, Chiral diphosphine/1,2-diamine-Ru(II) complexes catalyse the rapid, productive and enantioselective hydrogenation of simple ketones. The carbonyl-selective hydrogenation takes place via a non-classical metal-ligand bifunctional mechanism. The reduction of the C=O function occurs in the outer coordination sphere of an 18e transRuH(2)(diphosphine)(diamine) complex without interaction between the unsaturated moiety and the metallic centre. The Ru atom donates a hydride and the NH2 ligand delivers a, proton through a pericyclic six-membered transition state, directly giving an alcoholic product without metal alkoxide formation. The enantiofaces of prochiral ketones are differentiated on the chiral molecular surface of the saturated RuH2 species. This asymmetric catalysis manifests the significance of 'kinetic' supramolecular chemistry.

Metal-ligand bifunctional catalysis for asymmetric hydrogenation
R Noyori, CA Sandoval, K Muniz, T Ohkuma
PHILOSOPHICAL TRANSACTIONS OF THE ROYAL SOCIETY A-MATHEMATICAL PHYSICAL AND ENGINEERING SCIENCES, 363, 1829, 901, 912, ROYAL SOCIETY, Apr. 2005, [Peer-reviewed]
English, Scientific journal, Chiral diphosphine/1,2-diamine-Ru(II) complexes catalyse the rapid, productive and enantioselective hydrogenation of simple ketones. The carbonyl-selective hydrogenation takes place via a non-classical metal-ligand bifunctional mechanism. The reduction of the C=O function occurs in the outer coordination sphere of an 18e transRuH(2)(diphosphine)(diamine) complex without interaction between the unsaturated moiety and the metallic centre. The Ru atom donates a hydride and the NH2 ligand delivers a, proton through a pericyclic six-membered transition state, directly giving an alcoholic product without metal alkoxide formation. The enantiofaces of prochiral ketones are differentiated on the chiral molecular surface of the saturated RuH2 species. This asymmetric catalysis manifests the significance of 'kinetic' supramolecular chemistry.

Preparation of the dibenz[c,g]azecine structure via ring-opening by singlet oxygen
WADA YASUHIRO, TOMIKI MIHO, TOKUDA MASAO, OKUMA TAKESHI, ORITO KAZUHIKO
日本化学会講演予稿集, 85th, 2, 937, 11 Mar. 2005
Japanese

Cyclization reactions for preparation of dibenzindolizine rings
WADA YASUHIRO, NISHIDA NAOTO, TOKUDA MASAO, OKUMA TAKESHI, ORITO KAZUHIKO
日本化学会講演予稿集, 85th, 2, 937, 11 Mar. 2005
Japanese

Direct aromatic carbonylation using Pd(OAc)2. Synthesis of benzo[c]phenanthridine alkaloids
KUMAZAWA ERI, TOKUHASHI TAKASHI, HORIBATA AKIYOSHI, OKUMA TSUYOSHI, TOKUDA MASAO, ORITO KAZUHIKO
複素環化学討論会講演要旨集, 34th, 229-230, 01 Nov. 2004
Japanese

Stereoselective and highly efficient cyclization using aminyl radical
MIKAMI JUN'YA, HASEGAWA HIKARU, KURONO NOBUHITO, OKUMA TAKESHI, ORITO KAZUHIKO, TOKUDA MASAO
複素環化学討論会講演要旨集, 34th, 231-232, 01 Nov. 2004
Japanese

BINAP/1 4-diamine-ruthenium(II) complexes for efficient asymmetric hydrogenation of 1-tetralones and analogues
T Ohkuma, T Hattori, H Ooka, T Inoue, R Noyori
ORGANIC LETTERS, 6, 16, 2681, 2683, AMER CHEMICAL SOC, Aug. 2004
English, Scientific journal, A combined system of a RuCl2(binap)(1,4-diamine) complex and t-C4H9OK in i-C3H7OH catalyzes enantioselective hydrogenation of various 1-tetralone derivatives and some methylated 2-cyclohexenones. Hydrogenation of 2-methyl-1-tetralone under dynamic kinetic resolution gives the cis alcohol with high ee.

BINAP/1 4-diamine-ruthenium(II) complexes for efficient asymmetric hydrogenation of 1-tetralones and analogues
T Ohkuma, T Hattori, H Ooka, T Inoue, R Noyori
ORGANIC LETTERS, 6, 16, 2681, 2683, AMER CHEMICAL SOC, Aug. 2004, [Peer-reviewed]
English, Scientific journal, A combined system of a RuCl2(binap)(1,4-diamine) complex and t-C4H9OK in i-C3H7OH catalyzes enantioselective hydrogenation of various 1-tetralone derivatives and some methylated 2-cyclohexenones. Hydrogenation of 2-methyl-1-tetralone under dynamic kinetic resolution gives the cis alcohol with high ee.

Asymmetric hydrogenation of 2-arylated cycloalkanones through dynamic kinetic resolution
T Ohkuma, J Li, R Noyori
SYNLETT, 8, 1383, 1386, GEORG THIEME VERLAG KG, Jul. 2004
English, Scientific journal, Asymmetric hydrogenation of 2-arylcycloalkanones with trans-RuCl2(binap)(1,2-diamine) and t-C4H9OK in 2-propanol selectively gives the corresponding cis-2-arylcycloalkanois in excellent enantiomeric purity and high yield. Two synthetic intermediates of biologically active compounds have been prepared by this method.

Toward efficient asymmetric hydrogenation: Architectural and functional engineering of chiral molecular catalysts
R Noyori, M Kitamura, T Ohkuma
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 101, 15, 5356, 5362, NATL ACAD SCIENCES, Apr. 2004
English, Scientific journal, Asymmetric hydrogenation uses inexpensive, clean hydrogen gas and a very small amount of a chiral molecular catalyst, providing the most powerful way to produce a wide array of enantio-enriched compounds in a large quantity without forming any waste. The recent revolutionary advances in this field have entirely changed the synthetic approach to producing performance chemicals that require a high degree of structural precision. The means of developing efficient asymmetric hydrogenations is discussed from a mechanistic point of view.

Toward efficient asymmetric hydrogenation: Architectural and functional engineering of chiral molecular catalysts
R Noyori, M Kitamura, T Ohkuma
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 101, 15, 5356, 5362, NATL ACAD SCIENCES, Apr. 2004, [Peer-reviewed]
English, Scientific journal, Asymmetric hydrogenation uses inexpensive, clean hydrogen gas and a very small amount of a chiral molecular catalyst, providing the most powerful way to produce a wide array of enantio-enriched compounds in a large quantity without forming any waste. The recent revolutionary advances in this field have entirely changed the synthetic approach to producing performance chemicals that require a high degree of structural precision. The means of developing efficient asymmetric hydrogenations is discussed from a mechanistic point of view.

Key chemicals that regulate unexplained biological phenomena. Synthesis of optically-active alcohols with physiological function.
Takeshi Ohkuma
未解明生物現象を司る鍵化学物質 平成11−14年度 No.11175101, 260-263, 2004
Japanese

CFTAエステルのNMR測定によるキラルアルコール類の絶対配置決定法
藤沢英仁, 藤原朋也, 竹内義雄, 大熊毅, 野依良治
フッ素化学討論会講演要旨集, 27th, 24-25, 20 Nov. 2003
Japanese

Mechanism of asymmetric hydrogenation of ketones catalyzed by BINAP/1,2-diamine-ruthenium(II) complexes
CA Sandoval, T Ohkuma, K Muniz, R Noyori
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 125, 44, 13490, 13503, AMER CHEMICAL SOC, Nov. 2003
English, Asymmetric hydrogenation of acetophenone with trans-RuH(eta(1)-BH4) [ (S)-tolbinap] [ (S, S)-dpen] (TolBINAP = 2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl; DPEN = 1,2-diphenylethylenediamine) in 2-propanol gives (R)-phenylethanol in 82% ee. The reaction proceeds smoothly even at an atmospheric pressure of H-2 at room temperature and is further accelerated by addition of an alkaline base or a strong organic base. Most importantly, the hydrogenation rate is initially increased to a great extent with an increase in base molarity but subsequently decreases. Without a base, the rate is independent of H-2 pressure in the range of 1-16 atm, while in the presence of a base, the reaction is accelerated with increasing H-2 pressure. The extent of enantioselection is unaffected by hydrogen pressure, the presence or absence of base, the kind of base and coexisting metallic or organic cations, the nature of the solvent, or the substrate concentrations. The reaction with H-2/(CH3)(2)CHOH proceeds 50 times faster than that with D-2/(CD3)(2)CDOD in the absence of base, but the rate differs only by a factor of 2 in the presence of KO-t-C4H9. These findings indicate that dual mechanisms are in operation, both of which are dependent on reaction conditions and involve heterolytic cleavage of H-2 to form a common reactive intermediate. The key [RuH(diphosphine)(diamine)] and its solvate complex have been detected by ESI-TOFMS and NMR spectroscopy. The hydrogenation of ketones is proposed to occur via a nonclassical metal-ligand bifunctional mechanism involving a chiral RuH2(diphosphine)(diamine), where a hydride on Ru and a proton of the NH2 ligand are simultaneously transferred to the C=O function via a six-membered pericyclic transition state. The NH2 unit in the diamine ligand plays a pivotal role in the catalysis. The reaction occurs in the outer coordination sphere of the 18e RuH2 complex without C=O/metal interaction. The enantiofaces of prochiral aromatic ketones are kinetically differentiated on the molecular surface of the coordinatively saturated chiral RuH2 intermediate rather than in a coordinatively unsaturated Ru template.

Mechanism of asymmetric hydrogenation of ketones catalyzed by BINAP/1,2-diamine-ruthenium(II) complexes
CA Sandoval, T Ohkuma, K Muniz, R Noyori
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 125, 44, 13490, 13503, AMER CHEMICAL SOC, Nov. 2003, [Peer-reviewed]
English, Asymmetric hydrogenation of acetophenone with trans-RuH(eta(1)-BH4) [ (S)-tolbinap] [ (S, S)-dpen] (TolBINAP = 2,2'-bis(di-4-tolylphosphino)-1,1'-binaphthyl; DPEN = 1,2-diphenylethylenediamine) in 2-propanol gives (R)-phenylethanol in 82% ee. The reaction proceeds smoothly even at an atmospheric pressure of H-2 at room temperature and is further accelerated by addition of an alkaline base or a strong organic base. Most importantly, the hydrogenation rate is initially increased to a great extent with an increase in base molarity but subsequently decreases. Without a base, the rate is independent of H-2 pressure in the range of 1-16 atm, while in the presence of a base, the reaction is accelerated with increasing H-2 pressure. The extent of enantioselection is unaffected by hydrogen pressure, the presence or absence of base, the kind of base and coexisting metallic or organic cations, the nature of the solvent, or the substrate concentrations. The reaction with H-2/(CH3)(2)CHOH proceeds 50 times faster than that with D-2/(CD3)(2)CDOD in the absence of base, but the rate differs only by a factor of 2 in the presence of KO-t-C4H9. These findings indicate that dual mechanisms are in operation, both of which are dependent on reaction conditions and involve heterolytic cleavage of H-2 to form a common reactive intermediate. The key [RuH(diphosphine)(diamine)] and its solvate complex have been detected by ESI-TOFMS and NMR spectroscopy. The hydrogenation of ketones is proposed to occur via a nonclassical metal-ligand bifunctional mechanism involving a chiral RuH2(diphosphine)(diamine), where a hydride on Ru and a proton of the NH2 ligand are simultaneously transferred to the C=O function via a six-membered pericyclic transition state. The NH2 unit in the diamine ligand plays a pivotal role in the catalysis. The reaction occurs in the outer coordination sphere of the 18e RuH2 complex without C=O/metal interaction. The enantiofaces of prochiral aromatic ketones are kinetically differentiated on the molecular surface of the coordinatively saturated chiral RuH2 intermediate rather than in a coordinatively unsaturated Ru template.

trans-RuH(eta(1)-BH4)(binap)(1,2-diamine): a catalyst for asymmetric hydrogenation of simple ketones under base-free conditions
T Ohkuma, M Koizumi, K Muniz, G Hilt, C Kabuto, R Noyori
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 124, 23, 6508, 6509, AMER CHEMICAL SOC, Jun. 2002, [Peer-reviewed]
English, Scientific journal

Noyori Laboratory:A Portrait of Saturday
Ohkuma Takeshi
tits, 7, 1, 80, 81, Japan Science Support Foundation, 2002
Japanese

ケトン類の高速かつ高立体選択的水素化反応 (特集 有機金属化学の新展開)
大熊 毅
化学工業, 52, 12, 951, 957, 化学工業社, Dec. 2001
Japanese

有機金属化学の新展開 ケトン類の高速かつ高立体選択的水素化反応
大熊毅
化学工業, 52, 12, 951-957, 979, 化学工業社, 01 Dec. 2001
Japanese

ケトン類の高速かつ高立体選択的水素化反応
大熊毅
日本化学会講演予稿集, 80th, 34, 07 Sep. 2001
Japanese

単純ケトン類の水素化触媒の開拓 : ユニークな触媒はユニークな発想から生まれる
大熊 毅
有機合成化学協会誌 : JOURNAL OF Synthetic Organic Chemistry JAPAN, 59, 5, 446, 447, 社団法人 有機合成化学協会, 01 May 2001
Japanese

単純ケトン類の水素化触媒の開拓 ユニークな触媒はユニークな発想から生まれる
大熊毅
有機合成化学協会誌, 59, 5, 446, 447, The Society of Synthetic Organic Chemistry, Japan, 01 May 2001
Japanese

Asymmetric hydrogenation of ketones with polymer-bound BINAP/diamine ruthenium catalysts
T Ohkuma, H Takeno, Y Honda, R Noyori
ADVANCED SYNTHESIS & CATALYSIS, 343, 4, 369, 375, WILEY-V C H VERLAG GMBH, May 2001, [Peer-reviewed]
English, Scientific journal, The BINAP/1,2-diphenylethylenediamine RuCl2 complexes bound to a polystyrene resin act as precatalysts for asymmetric hydrogenation of various simple ketones. The enantioselectivity, turnover number, and turnover frequency are comparable to those attained under homogeneous conditions.

General Asymmetric Hydrogenation of Hetero-aromatic Ketones.
OKUMA TAKESHI, KOIZUMI MASATOSHI, YOSHIDA MAKOTO, NOYORI RYOJI
日本化学会講演予稿集, 79th, 2, 1201, 15 Mar. 2001
Japanese

Asymmetric Hydrogenation of Amino and Alkoxy Ketones Using Chiral RuCl2(diphosphine)(1,2-diamine) Complexes.
OKUMA TAKESHI, ISHII DAI, TAKENO HIROSHI, NOYORI RYOJI
日本化学会講演予稿集, 79th, 2, 1201, 15 Mar. 2001
Japanese

Asymmetric Hydrogenation of .ALPHA.-Ethylstyrenes Catalyzed by Chiral Ruthenium Complexes.
FORMAN G S, OKUMA TAKESHI, HEMS W P, NOYORI RYOJI
日本化学会講演予稿集, 79th, 2, 1201, 15 Mar. 2001
Japanese

Asymmetric hydrogenation via architectural and functional molecular engineering
R Noyori, M Koizumi, D Ishii, T Ohkuma
PURE AND APPLIED CHEMISTRY, 73, 2, 227, 232, INT UNION PURE APPLIED CHEMISTRY, Feb. 2001, [Peer-reviewed]
English, Scientific journal, RuCl2(phosphine)(2)(1,2-diamine) complexes, coupled with an alkaline base in 2-propanol, allows for preferential hydrogenation of a C=O function over coexisting conjugated or nonconjugated C=C linkages, a nitro group, halogen atoms, and various heterocycles. The functional group selectivity is based on the novel metal-ligand bifunctional mechanism. The use of appropriate chiral diphosphines and diamines results in rapid and productive asymmetric hydrogenation of a range of aromatic, hetero-aromatic, and olefinic ketones. The versatility of this method is manifested by the asymmetric synthesis of various biologically significant chiral compounds.

Asymmetric catalysis by architectural and functional molecular engineering: Practical chemo- and stereoselective hydrogenation of ketones
R Noyori, T Ohkuma
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 40, 1, 40, 73, WILEY-BLACKWELL, 2001, [Peer-reviewed]
English

Asymmetric hydrogenation of alpha-ethylstyrenes catalyzed by chiral ruthenium complexes
GS Forman, T Ohkuma, WP Hems, R Noyori
TETRAHEDRON LETTERS, 41, 49, 9471, 9475, PERGAMON-ELSEVIER SCIENCE LTD, Dec. 2000, [Peer-reviewed]
English, Scientific journal, A combined system of RuCl2[ (R,R)-Me-DuPhos](dmf)(n) and t-C4H9OK catalyzes the asymmetric hydrogenation of alpha -ethylstyrene derivatives. The reaction proceeds with a substrate to catalyst molar ratio of up to 2600 in 2-propanol at 8 atm and room temperature to give the chiral saturated products in 81-89% ee. (C) 2000 Elsevier Science Ltd. All rights reserved.

Asymmetric hydrogenation of amino ketones using chiral RuCl2(diphophine)(1,2-diamine) complexes
T Ohkuma, D Ishii, H Takeno, R Noyori
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 122, 27, 6510, 6511, AMER CHEMICAL SOC, Jul. 2000, [Peer-reviewed]
English, Scientific journal

General asymmetric hydrogenation of hetero-aromatic ketones
T Ohkuma, M Koizumi, M Yoshida, R Noyori
ORGANIC LETTERS, 2, 12, 1749, 1751, AMER CHEMICAL SOC, Jun. 2000, [Peer-reviewed]
English, Scientific journal, [GRAPHICS]
trans-RuCL2[ (R)-xylbinap][ (R)-daipen] or the S,S complex acts as an efficient catalyst for asymmetric hydrogenation of hetero-aromatic ketones. The hydrogenation proceeds with a substrate-to-catalyst molar ratio of 1000-40000 to give chiral alcohols in high ee and high yield. The enantioselectivity appears to be little affected by the properties of the hetero-aromatic ring. This method allows for asymmetric synthesis of duloxetine, an inhibitor of serotonin and norepinephrine uptake carriers.

Enantioselective Hydrogenation of Benzophenones with trans-RuCl2(xylbinap)(daipen) as a Precatalyst.
OKUMA TAKESHI, KOIZUMI MASATOSHI, IKEHIRA HIDEYUKI, YOKOZAWA TOORU, NOYORI RYOJI
日本化学会講演予稿集, 78th, 2, 1043, 15 Mar. 2000
Japanese

Selective hydrogenation of benzophenones to benzhydrols. Asymmetric synthesis of unsymmetrical diarylmethanols
T Ohkuma, M Koizumi, H Ikehira, T Yokozawa, R Noyori
ORGANIC LETTERS, 2, 5, 659, 662, AMER CHEMICAL SOC, Mar. 2000, [Peer-reviewed]
English, Scientific journal, [GRAPHICS]
trans-RuCl2[P(C6H4-4-CH3)(3)](2)(NH2CH2CH2NH2) acts as a highly effective precatalyst for the hydrogenation of a variety of benzophenone derivatives to benzhydrols that proceeds smoothly at 8 atm and 23-35 degrees C in 2-propanol containing t-C4H9OK with a substrate/catalyst ratio of 2000-20000. Use of a BINAP/chiral diamine Ru complex effects asymmetric hydrogenation of various ortho-substituted benzophenones and benzoylferrocene to chiral diarylmethanols with consistently high ee.

Asymmetric activation/deactivation of racemic Ru catalysts for highly enantioselective hydrogenation of ketonic substrates
K Mikami, T Korenaga, T Ohkuma, R Noyori
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 39, 20, 3707, 3710, WILEY-V C H VERLAG GMBH, 2000, [Peer-reviewed]
English, Scientific journal

単純ケトン類の不斉水素化反応
大熊毅
日本化学会講演予稿集, 77th, 155, 10 Sep. 1999
Japanese

High-speed and highly stereoselective hydrogenation of simple ketones
T Ohkuma
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN, 57, 8, 667, 676, SOC SYNTHETIC ORGANIC CHEM JPN, Aug. 1999
Japanese, Hydrogenation of ketones is amongst one of the most important synthetic reactions. This transformation is not only of academic interest, but also of industrial significance because of its simplicity, environmentally friendliness, and economic viability. trans-RuCl2 (phosphine)(2)(1,2-diamine), when coupled with a strong base in 2-propanol, acts as the most reactive catalyst for homogeneous hydrogenation of ketones. This reaction, unlike conventional hydrogenation, proceeds selectively at a C=O bond leaving coexisting C=C linkages intact. Furthermore, rapid, highly productive asymmetric hydrogenation of simple ketones has been realized by using trans-RuCl2[ (S)-tolbinap] [ (S, S)-dpen] or its optical antipode. When acetophenone is hydrogenated with the complex, the turnover number reaches 2,400,000 and the turnover frequency as high as 228,000 h(-1) or 63 s(-1). When XylBINAP is used as a chiral phosphine, a wide variety of prochiral ketones are hydrogenated in up to 100% ee. This practical asymmetric hydrogenation will greatly facilitate the synthesis of biologically active compounds and functional materials.

Rapid, productive and stereoselective hydrogenation of ketones
R Noyori, T Ohkuma
PURE AND APPLIED CHEMISTRY, 71, 8, 1493, 1501, BLACKWELL SCIENCE LTD, Aug. 1999, [Peer-reviewed]
English, Scientific journal, RuCl2(phosphine)(2)(1,2-diamine) complexes act as excellent precatalysts for homogeneous hydrogenation of simple ketones which lack any functionality capable of interacting with the metallic center. This newly devised catalytic system allows preferential saturation of a C=O function over a coexisting C=C linkage in 2-propanol containing an alkaline base. Furthermore, the stereoselectivity of the reaction is easily controlled by the electronic and steric properties (bulkiness and chirality) of the ligands as well as the reaction conditions.

単純ケトン類の水素化反応 高活性と高立体選択性をめざして
大熊毅
万有製薬株式会社札幌シンポジウム要旨集, 11th, 1-6, 19 Jul. 1999
Japanese

Molecule catalyst of which it is the most efficient.
OKUMA TAKESHI
別冊化学, 1999, 111-115, 01 May 1999
Japanese

Asymmetric Hydrogenation of .ALPHA.,.BETA.-Unsaturated Ketones with trans-RuCl2(xylbinap)(1,2-diamine).
OKUMA TAKESHI, KOIZUMI MASATOSHI, DOUCET H, PHAM T, KOZAWA MASAMI, MURATA KUNIHIKO, KATAYAMA EIJI, YOKOZAWA TOORU, NOYORI RYOJI
日本化学会講演予稿集, 76th, 2, 899, 15 Mar. 1999
Japanese

Highly Efficient Asymmetric Hydrogenation of Aromatic Ketones with trans-RuCl2(xylbinap)(1,2-diamine).
OKUMA TAKESHI, KOIZUMI MASATOSHI, DOUCET H, PHAM T, KOZAWA MASAMI, MURATA KUNIHIKO, KATAYAMA EIJI, YOKOZAWA TOORU, NOYORI RYOJI
日本化学会講演予稿集, 76th, 2, 898, 15 Mar. 1999
Japanese

Stereoselective Hydrogenation of Simple Ketones.
OKUMA TAKESHI
日本化学会講演予稿集, 76th, 2, 969, 15 Mar. 1999
Japanese

Conformationally flexible biphenylphosphane ligands for Ru-catalyzed enantioselective hydrogenation
K Mikami, T Korenaga, M Terada, T Ohkuma, T Pham, R Noyori
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 38, 4, 495, 497, WILEY-V C H VERLAG GMBH, 1999, [Peer-reviewed]
English, Scientific journal

Asymmetric hydrogenation of alkenyl, cyclopropyl, and aryl ketones. RuCl2(xylbinap)(1,2-diamine) as a precatalyst exhibiting a wide scope
T Ohkuma, M Koizumi, H Doucet, T Pham, M Kozawa, K Murata, E Katayama, T Yokozawa, T Ikariya, R Noyori
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 120, 51, 13529, 13530, AMER CHEMICAL SOC, Dec. 1998, [Peer-reviewed]
English, Scientific journal

Chemistry friendly with environment. Stereoselective hydrogenation reaction of simple ketone.
OKUMA TAKESHI
ファルマシア, 34, 11, 1095-1099, Nov. 1998
Japanese

単純ケトン類の立体選択的水素化反応
大熊 毅
ファルマシア, 34, 11, 1095, 1099, 公益社団法人日本薬学会, 01 Nov. 1998
Japanese

Synthesis of trans-RuCl2(1,2-diamine)(phosphine)2 and trans-RuCl2(1,2-diamine)(diphosphine).
HENRI D, OKUMA TAKESHI, MURATA KUNIHIKO, KOZAWA MASAMI, YOKOZAWA TOORU, KATAYAMA EIJI, IKARIYA TAKAO, NOYORI RYOJI
日本化学会講演予稿集, 74th, 2, 1071, Mar. 1998
Japanese

Hydrogenation of Benzophenones to Benzhydrols.
OKUMA TAKESHI, IKEHIRA HIDEYUKI, IKARIYA TAKAO, NOYORI RYOJI
日本化学会講演予稿集, 74th, 2, 1072, Mar. 1998
Japanese

Stereoselective Hydrogenation of Ketones with 1,2-Diamine-Phosphine-Ruthenium(II) Complexes.
HENRI D, OKUMA TAKESHI, MURATA KUNIHIKO, KOZAWA MASAMI, YOKOZAWA TOORU, KATAYAMA EIJI, IKARIYA TAKAO, NOYORI RYOJI
日本化学会講演予稿集, 74th, 2, 1072, Mar. 1998
Japanese

Asymmetric Activation of Racemic Ruthenium(II) Complexes for Enantioselective Hydrogenation.
OKUMA TAKESHI, HENRI D, PHAM T, NOYORI RYOJI
日本化学会講演予稿集, 74th, 2, 1071, Mar. 1998
Japanese

Asymmetric activation of racemic ruthenium(II) complexes for enantioselective hydrogenation
T Ohkuma, H Doucet, T Pham, K Mikami, T Korenaga, M Terada, R Noyori
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 120, 5, 1086, 1087, AMER CHEMICAL SOC, Feb. 1998, [Peer-reviewed]
English, Scientific journal

Asymmetric hydrogenation of cyclic alpha,beta-unsaturated ketones to chiral allylic alcohols
T Ohkuma, H Ikehira, T Ikariya, R Noyori
SYNLETT, 5, 467, +, GEORG THIEME VERLAG KG, May 1997, [Peer-reviewed]
English, Scientific journal, The Ru(II)-BINAP-1,2-diphenylethylenediamine combined catalyst system effects asymmetric hydrogenation of certain cyclic enones in 2-propanol containing KOH with a substrate/catalyst molar ratio of 250 to 2500. The hydrogenation occurs selectively at the C=O function with excellent enantio- or diastereoselectivity.

Asymmetric Hydrogenation of Cyclic .ALPHA.,.BETA.-Unsaturated Ketones to Chiral Allylic Alcohols.
OKUMA TAKESHI, IKEHIRA HIDEYUKI, IKARIYA TAKAO, NOYORI RYOJI
日本化学会講演予稿集, 72nd, 2, 809, Mar. 1997
Japanese

Practical stereoselective synthesis of trans-3-isocamphylcyclohexanol as a sandalwood odor principle.
EMURA MAKOTO, HARADA MAKOTO, TOYODA TAKAAKI, YAMAZAKI TETSURO, OKUMA TAKESHI, IKARIYA TAKAO, NOYORI RYOJI
日本化学会講演予稿集, 72nd, 2, 970, Mar. 1997
Japanese

Enantioselective hydrogenation of simple ketones
T Ohkuma, R Noyori
JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN, 54, 7, 553, 563, SOC SYNTHETIC ORGANIC CHEM JPN, Jul. 1996
Japanese, Scientific journal, Enantioselective reduction of prochiral ketones to optically active secondary alcohols is an important, fundamental subject in synthetic organic chemistry, because the resulting chiral alcohols are versatile building blocks for synthesis of natural or unnatural biological active compounds as well as functional materials. Asymmetric hydrogenation is particularly useful for a large-scale reduction because of the operational simplicity, economical advantage, and environmental consciousness. Enantioselective hydrogenation of simple ketones which have no heteroatoms near carbonyl groups has remained difficult. This review describes the recent development in this area. Certain chiral Ru(II) complexes exhibit an excellent catalytic activity and enantiodifferentiation ability in asymmetric hydrogenation of simple ketones in homogeneous phase.

カチオン性錯体,アニオン性錯体,中性錯体
大熊 毅
有機合成化学協会誌, 54, 7, 623, 623, 社団法人 有機合成化学協会, 01 Jul. 1996
Japanese

Diastereoselective Hydrogenation of Ketones Catalyzed by a RuCl2(phosphine)n-1,2-Diamine-KOH Combined System.
OKUMA TAKESHI, OOKA HIROHITO, IKARIYA TAKAO, NOYORI RYOJI
日本化学会講演予稿集, 70th, 2, 1310, Mar. 1996
Japanese

Preferential Hydrogenation of Aldehydes and Ketones.
OKUMA TAKESHI, OOKA HIROHITO, IKARIYA TAKAO, NOYORI RYOJI
日本化学会講演予稿集, 70th, 2, 1309, Mar. 1996
Japanese

Practical asymmetry hydrogenation reaction of ketones.
OKUMA TAKESHI
日本化学会中国四国支部岡山地区化学講演会講演要旨集, 1995, 1,2,3,4, Nov. 1995
Japanese

A Practical Enantioselective Hydrogenation of Aromatic Ketones.
OKUMA TAKESHI, OOKA HIROHITO, HASHIGUCHI SHOHEI, IKARIYA TAKAO, NOYORI RYOJI
日本化学会講演予稿集, 69th, 2, 1149, Mar. 1995
Japanese

A High Speed Hydrogenation of Ketones Catalyzed by Ruthenium Complex with Mixed Ligands.
OKUMA TAKESHI, OOKA HIROHITO, HASHIGUCHI SHOHEI, IKARIYA TAKAO, NOYORI RYOJI
日本化学会講演予稿集, 69th, 2, 1149, Mar. 1995
Japanese

A Practical Enantioselective Hydrogenation of Aromatic Ketones.
OKUMA TAKESHI
創造科学技術推進事業 1994 創造科学技術研究報告会(東京) 第4部講演要旨集, 85-89, 1994
Japanese

A PRACTICAL METHOD FOR ACTIVATION OF COMMERCIAL LITHIUM HYDRIDE - REDUCTIVE SILYLATION OF CARBONYL-COMPOUNDS WITH LITHIUM HYDRIDE AND CHLOROTRIMETHYLSILANE
T OHKUMA, S HASHIGUCHI, R NOYORI
JOURNAL OF ORGANIC CHEMISTRY, 59, 1, 217, 221, AMER CHEMICAL SOC, Jan. 1994, [Peer-reviewed]
English, Scientific journal, Commercially available lithium hydride, an essentially inert metal hydride, can be activated as a hydride source by an equimolar amount of chlorotrimethylsilane and a catalytic amount of a Zn salt or Zn powder. Aromatic and aliphatic ketones, as well as nonenolizable aldehydes, are reductively converted to the trimethylsilyl ethers of the corresponding alcohols in high yields by treatment with this reagent system in dichloromethane or toluene at 28 to 40 degrees C for 25-50 h. This procedure has many advantages including the safety and low cost of the reagents and operational simplicity and provides a practical method for carbonyl reduction. X-ray induced Auger electron spectroscopy analysis suggests that a Zn(II)I species is the catalyst of the heterogeneous reaction.

不斉水素化に有効なBINAP‐Ru(II)錯体触媒の簡易合成
北村雅人, 徳永信, 大熊毅, 野依良治
日本化学会講演予稿集, 62nd, 2, 611, Sep. 1991
Japanese

4位置換γ‐ラクトン類のエナンチオ選択的合成
大熊毅, 北村雅人, 野依良治
日本化学会講演予稿集, 61st, 2, 1485, Mar. 1991
Japanese

ENANTIOSELECTIVE SYNTHESIS OF 4-SUBSTITUTED GAMMA-LACTONES
T OHKUMA, M KITAMURA, R NOYORI
TETRAHEDRON LETTERS, 31, 38, 5509, 5512, PERGAMON-ELSEVIER SCIENCE LTD, 1990, [Peer-reviewed]
English, Scientific journal

74 CATALYTIC ASYMMETRIC HYDROGENATION OF FUNCTIONALIZED KETONES
Kitamura M, Ohkuma T, Nishi T, Takaya H, Noyori R
Symposium on the Chemistry of Natural Products, symposium papers, 0, 30, 572, 579, Symposium on the chemistry of natural products, 26 Sep. 1988
Japanese, Under the influence of the (R)- or (S)-BINAP-based Ru(II) complexes (BINAP =2,2'-bis(diphenylphosphino)-1,1'-binaphthyl), a wide range of functionalized ketones are hydrogenated in a highly enantioselective and predictable manner. The hydrogenation proceeds smoothly in alcoholic media at room temperature with initial hydrogen pressure of 40-100 atm. The substrate to catalyst mole ratio ranges from 230 to 2200. Ru complexes of the type RuX_2(binap) (X = halogen, empirical formula), Ru_2Cl_4(binap)_2N(C_2H_5)_3, or Ru(OCOR)_2(binap) are employable as catalysts, depending on the substrates. Va...

1,3-ジオ-ル類の立体選択的合成 (1988年の化学-7-)
大熊 毅, 野依 良治
化学, 43, 7, p480, 481, 化学同人, Jul. 1988
Japanese

Stereoselective synthesis of 1,3-diols.
OHKUMA TAKESHI, NOYORI RYOJI
化学, 43, 7, 480-481, Jul. 1988
Japanese

PB83 A PRACTICAL ASYMMETRIC SYNTHESIS OF CARNITINE
Kitamura M., Ohkuma T., Takaya H., Noyori R.
International Symposium on the Chemistry of Natural Products, 1988, 329, 329, Symposium on the chemistry of natural products, 29 May 1988
English

A PRACTICAL ASYMMETRIC-SYNTHESIS OF CARNITINE
M KITAMURA, T OHKUMA, H TAKAYA, R NOYORI
TETRAHEDRON LETTERS, 29, 13, 1555, 1556, PERGAMON-ELSEVIER SCIENCE LTD, 1988, [Peer-reviewed]
English, Scientific journal

SYNTHESIS OF STATINE AND ITS ANALOGS BY HOMOGENEOUS ASYMMETRIC HYDROGENATION
T NISHI, M KITAMURA, T OHKUMA, R NOYORI
TETRAHEDRON LETTERS, 29, 48, 6327, 6330, PERGAMON-ELSEVIER SCIENCE LTD, 1988, [Peer-reviewed]
English, Scientific journal

ASYMMETRIC-SYNTHESIS OF CHIRAL SYNTHONS BEARING ALKYNYL GROUP VIA ORGANOALUMINUM-PROMOTED PINACOL-TYPE REARRANGEMENT
K SUZUKI, T OHKUMA, M MIYAZAWA, GI TSUCHIHASHI
TETRAHEDRON LETTERS, 27, 3, 373, 376, PERGAMON-ELSEVIER SCIENCE LTD, 1986, [Peer-reviewed]
English, Scientific journal

ENANTIO-CONTROLLED AND DIASTEREO-CONTROLLED SYNTHESIS OF (+)-ELDANOLIDE AND (-)-ELDANOLIDE BASED ON ASYMMETRIC PINACOL-TYPE REARRANGEMENT
K SUZUKI, T OHKUMA, G TSUCHIHASHI
TETRAHEDRON LETTERS, 26, 7, 861, 864, PERGAMON-ELSEVIER SCIENCE LTD, 1985, [Peer-reviewed]
English, Scientific journal

Asymmetric Hydrogenaton of Polysubstituted Aromatic Ketones Catalyzed by the DIPSkewphos/PICA Derivative–Ruthenium(II) Complexes　　　　　　　　　　　　　　　
N. Utsmi, N. Arai, K. Kawaguchi, T. Katayama, T. Yasuda, K. Murata, T. Ohkuma
ChemCatChem, Publishaed, on Web, [Peer-reviewed]
English, Scientific journal

Synthesis of 8-Oxoberbines and Related Benzolactams by Pd(OAc)2-Catalyzed Direct Aromatic Carbonylation　　　　　　　　　　　　　　　
M. Miyazawa, T. Tokuhashi, A. Horibata, T. Nakamura, Y. Onozaki, N. Kurono, H. Senboku, M. Tokuda, T. Ohkuma, K. Orito
[Peer-reviewed]

Enantioresolution and absolute stereochemistry of o-substituted diphenylmethanols
S Kuwahara, M Watanabe, N Harada, M Koizumi, T Ohkuma, ENANTIOMER, 5, 1, 109, 114, 2000
o-Substituted diphenylmethanols were enantioresolved by the method of chiral dichlorophthalic acid amide, yielding enantiopure alcohols. Their absolute configurations were unambiguously determined by X-ray crystallography of chiral dichlorophthalate esters., GORDON BREACH SCI PUBL LTD, English

Enantioresolution by the chiral phthalic acid method: absolute configurations of (2-methylphenyl)phenylmethanol and related compounds
M Watanabe, S Kuwahara, N Harada, M Koizumi, T Ohkuma, TETRAHEDRON-ASYMMETRY, 10, 11, 2075, 2078, Jun. 1999
Racemic (2-hydroxymethylphenyl)phenylmethanol 5 was enantioresolved by the chiral phthalic acid method using acid-amide 2, and the absolute configurations of (-)-(2-methylphenyl)phenylmethanol 3 and related o-substituted diphenylmethanol derivatives were unambiguously determined by X-ray crystallography and chemical correlation. (C) 1999 Elsevier Science Ltd. All rights reserved., PERGAMON-ELSEVIER SCIENCE LTD, English

trans-[RuCl(2)(phosphane)(2)(1,2-diamine)] and chiral trans-[RuCl(2)(diphosphane)(1,2-diamine]): Shelf-stable precatalysts for the rapid, productive, and stereoselective hydrogenation of ketones
H Doucet, T Ohkuma, K Murata, T Yokozawa, M Kozawa, E Katayama, AF England, T Ikariya, R Noyori, ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 37, 12, 1703, 1707, Jul. 1998
WILEY-BLACKWELL, English

Stereoselective hydrogenation of simple ketones catalyzed by Ruthenium(II) complexes
T Ohkuma, H Ooka, M Yamakawa, T Ikariya, R Noyori, JOURNAL OF ORGANIC CHEMISTRY, 61, 15, 4872, 4873, Jul. 1996
AMER CHEMICAL SOC, English, Report scientific journal

On the mechanism of the ruthenium catalyzed hydrogenation of simple aromatic ketones
AF England, T Ohkuma, T Ikariya, R Noyori, ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 211, 523, INOR, Mar. 1996
AMER CHEMICAL SOC, English, Summary international conference

PREFERENTIAL HYDROGENATION OF ALDEHYDES AND KETONES
T OHKUMA, H OOKA, T IKARIYA, R NOYORI, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 117, 41, 10417, 10418, Oct. 1995
AMER CHEMICAL SOC, English, Introduction scientific journal

アルデヒドおよびケトンの優先的水素化
OHKUMA T, OOKA H, IKARIYA T, NOYORI R, Journal of the American Chemical Society, 117, 41, 10417, 10418, 1995

CONVENIENT PREPARATION OF BINAP RUTHENIUM(II) COMPLEXES CATALYZING ASYMMETRIC HYDROGENATION OF FUNCTIONALIZED KETONES
M KITAMURA, M TOKUNAGA, T OHKUMA, R NOYORI, TETRAHEDRON LETTERS, 32, 33, 4163, 4166, Aug. 1991
Ligand exchange between [RuCl2(benzene)]2 or RuCl2[Sb(C6H5)3]3 and (R)- or (S)-BINAP produces BINAP-Ru(II) complexes which act as catalysts for the highly enantioselective hydrogenation of functionalized ketones., PERGAMON-ELSEVIER SCIENCE LTD, English

DYNAMIC KINETIC RESOLUTION IN BINAP-RUTHENIUM(II) CATALYZED HYDROGENATION OF 2-SUBSTITUTED 3-OXO CARBOXYLIC ESTERS
M KITAMURA, T OHKUMA, M TOKUNAGA, R NOYORI, TETRAHEDRON-ASYMMETRY, 1, 1, 1, 4, 1990
BINAP-Ru catalyzed hydrogenation allows efficient dynamic kinetic resolution of certain 2-substituted 3-oxo carboxylic esters having cyclic structures to lead to the alcoholic products in high enantiomeric and diastereomeric excesses. © 1991., PERGAMON-ELSEVIER SCIENCE LTD, English, Introduction scientific journal

STEREOSELECTIVE HYDROGENATION VIA DYNAMIC KINETIC RESOLUTION
R NOYORI, T IKEDA, T OHKUMA, M WIDHALM, M KITAMURA, H TAKAYA, S AKUTAGAWA, N SAYO, T SAITO, T TAKETOMI, H KUMOBAYASHI, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 111, 25, 9134, 9135, Dec. 1989
AMER CHEMICAL SOC, English, Introduction scientific journal

HOMOGENEOUS ASYMMETRIC HYDROGENATION OF FUNCTIONALIZED KETONES
M KITAMURA, T OHKUMA, S INOUE, N SAYO, H KUMOBAYASHI, S AKUTAGAWA, T OHTA, H TAKAYA, R NOYORI, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 110, 2, 629, 631, Jan. 1988
AMER CHEMICAL SOC, English, Introduction scientific journal

ASYMMETRIC HYDROGENATION OF BETA-KETO CARBOXYLIC ESTERS - A PRACTICAL, PURELY CHEMICAL ACCESS TO BETA-HYDROXY ESTERS IN HIGH ENANTIOMERIC PURITY
R NOYORI, T OHKUMA, M KITAMURA, H TAKAYA, N SAYO, H KUMOBAYASHI, S AKUTAGAWA, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 109, 19, 5856, 5858, Sep. 1987
AMER CHEMICAL SOC, English, Introduction scientific journal

PREPARATION OF ENAMINONES BY 2-CARBON HOMOLOGATION OF AMIDES WITH LITHIUM (TRIPHENYLSILYL)ACETYLIDE
K SUZUKI, T OHKUMA, G TSUCHIHASHI, JOURNAL OF ORGANIC CHEMISTRY, 52, 13, 2929, 2930, Jun. 1987
AMER CHEMICAL SOC, English, Introduction scientific journal

Comprehensive Chirality, 2nd edition, Vol. 7
Takeshi Ohkuma, Introduction
Elsevier • Academic Press, May 2024, 9780323906449, 1, English, Scholarly book, 46744024, [Peer-reviewed], [Contributor]

Comprehensive Chirality, 2nd edition, Vol. 7　　　　　　　　　　　　　　　
Taiga Yurino, Takeshi Ohkuma, Reduction: Asymmetric Hydorgenation and Transfer Hydrogenation of C=O Bonds.
Elsevier: Academic Press, May 2024, 9780323906449, 43, English, Scholarly book, [Peer-reviewed], [Contributor]

ドラマチック有機合成化学 : 感動の瞬間100
有機合成化学協会, ケトンの高活性不斉水素化触媒を求めて—遷移状態モデルに基づいた試行錯誤—
化学同人, Jul. 2023, 9784759823363, xiv, 206p, Japanese, [Contributor]

有機合成のための新触媒反応101
百合野 大雅, 大熊 毅(有機合成化学協会, 檜山, 為次郎, 野崎, 京子, 中尾, 佳亮, 中野, 幸司 編集), カルボニル基のシアノ化; アルケン，アルキンのシアノ官能基化; 不斉Strecker反応
東京化学同人, Nov. 2021, 9784807920051, x, 212p, Japanese

Asymmetric Hydrogenation and Transfer Hydrogenation
Noriyoshi Arai, Takeshi Ohkuma, Asymmetric (Transfer) Hydrogenation of Functionalized Ketones
Wiley-VCH, Apr. 2021, 13483696, [Contributor]

化学便覧 基礎編 改定６版
新井則義, 大熊 毅, 12.10.3 水素化・水素移動反応 (https://www.chem-reference.com/viewkiso.php?ID=H120028)
丸善, 2020, 13483696, [Joint work]

Atropisomerism and Axial Chirality　　　　　　　　　　　　　　　
Taiga Kurino, Takeshi Ohkuma, Axially Chiral P,P-Ligands for Asymmetric Metal-Catalyzed Reactions
World Scientific, 2019, [Joint work]

Handbook of Organic Synthesis Experiment　　　　　　　　　　　　　　　
N. Arai, T. Ohkuma, Reduction with Gaseous Hydrogen
Maruzen, 2015, [Contributor]

Comprehensive Chirality, Vol. 5　　　　　　　　　　　　　　　
Ohkuma T, Arai N, Reduction–Hydrogenation: C=O; Chemoselective.
Elsevier, 2012, [Contributor]

Privileged Chiral Ligands and Catalysts　　　　　　　　　　　　　　　
Ohkuma T, Kurono N, BINAP
Wiley-VCH, 2011, [Contributor]

Science of Synthesis: Stereoselective Synthesis 2　　　　　　　　　　　　　　　
Arai N, Ohkuma T, Reduction of Carbonyl Compound: Hydrogenation.
Thieme, 2010, [Contributor]

分子集合体型錯体触媒を用いるケトン類およびイミン類の不斉水素化
大熊 毅
[北海道大学大学院工学研究科], 2008

Modern Reduction Methods　　　　　　　　　　　　　　　
Arai N, Ohkuma T, Carbonyl Hydroboration.
Wiley-VCH, 2008, [Contributor]

New Frontiers in Asymmetric Catalysis　　　　　　　　　　　　　　　
Ohkuma T, Kitamura M, Noyori R, Ligand Design for Catalytic Asymmetric Reduction.
John Wiley & Sons, Inc., 2007, [Contributor]

The Handbook of Homogeneous Hydrogenation　　　　　　　　　　　　　　　
Ohkuma T, Noyori R, Enantioselective Ketone and β-Keto Ester Hydrogenation (Including Mechanisms).
Wiley-VCH Verlag GmbH & Co. KGaA, 2007, [Contributor]

ケトン類の不斉水素化機構の解明
大熊 毅
[北海道大学大学院工学研究科], 2005

実力養成化学スクール キラル化学　　　　　　　　　　　　　　　
丸善, 2005

Chirality on Organic Chemistry　　　　　　　　　　　　　　　
Maruzen, 2005

化学便覧 基礎編II 第５版　　　　　　　　　　　　　　　
丸善, 2004

実験化学講座 第５版 第１９巻 有機化合物の合成VII　　　　　　　　　　　　　　　
丸善, 2004

Comprehensive Asymmetric Catalysis-Supplement 2　　　　　　　　　　　　　　　
Springer, 2004

Transition Metals for Organic Synthesis, 2nd Ed　　　　　　　　　　　　　　　
Wiley-VCH, 2004

有機合成のための触媒反応103　　　　　　　　　　　　　　　
東京化学同人, 2004

The Fifth Series of Chemistry Handbook　　　　　　　　　　　　　　　
Marzen, 2004

The Fifth Series of Experimental Chemistry　　　　　　　　　　　　　　　
Marzen, 2004

Catalytic Organic Reactions　　　　　　　　　　　　　　　
Tokyo Kagaku Dozin, 2004

ケトン類およびオレフィン類の不斉水素化
大熊 毅
[出版者不明], 2003

Comprehensive Asymmetric Catalysis-Supplement 1　　　　　　　　　　　　　　　
Springer, 2003

Handbook of Reagints for Organic Synthesis: Chiral Reagents for Asymmetric Synthesis　　　　　　　　　　　　　　　
John Wiley & Sons, Inc., 2003

ケトン類のエナンチオ選択的水素化反応
大熊 毅
[出版者不明], 2001

Development of Asymmetric Hydrogenation Catalyzed by Ruthenium Complexes with Two Kinds of Ligands
Takeshi Ohkuma
Wender Fest 2024@Tokyo, 08 Jun. 2024, English, Invited oral presentation
08 Jun. 2024 - 08 Jun. 2024, 46744024, [Invited]

Development of Regio- and Stereoselective Reactions Catalyzed by Metal Complexes　　　　　　　　　　　　　　　
Takeshi Ohkuma
日産化学株式会社 物質科学研究所 講演会, 24 Jul. 2023, Japanese, Invited oral presentation
24 Jul. 2023 - 24 Jul. 2023, [Invited]

Asymmetric Hydrogenation of Simple Ketones　　　　　　　　　　　　　　　
Takeshi Ohkuma
Commemorative Symposium on Citation for Chemical Breakthrough, 02 Jul. 2022, Japanese, Invited oral presentation
02 Jul. 2022, [Invited]

Catalytic Nucleophilic Isocyanation with Pd and Ad Catalysts　　　　　　　　　　　　　　　
Takeshi Okuma
Catalysts Asia-Pacific Academic Forum 2021, 08 Jul. 2021, English, Invited oral presentation
08 Jul. 2021 - 08 Jul. 2021, [Invited]

オープニング（オーガナイザー）　　　　　　　　　　　　　　　
大熊毅
第３２回札幌万有シンポジウム, 12 Dec. 2020, Japanese, Others
12 Dec. 2020 - 12 Dec. 2020, [Invited]

Recent Progress on Asymmetric Hydrogenation with Diphosphine/Diamine–Ru(II) Catalysts　　　　　　　　　　　　　　　
Takeshi Ohkuma
2019 Hokkaido University & Peking University Joint Symposium, 21 Jan. 2019, English, Invited oral presentation
[Invited], [International presentation]

Asymmetric Reactions Catalyzed by Chiral Ruthenium Complexes　　　　　　　　　　　　　　　
Takeshi Ohkuma
Yamaguchi University IoL Center Colloquium, 20 Nov. 2018, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

Development of Asymmetric Reactions Catalyzed by Chiral Ruthenium Complexes with Two Kinds of Ligands　　　　　　　　　　　　　　　
Takeshi Ohkuma
The98th the Chemical Society of Japan Annual Meeting, 20 Mar. 2018, English, Invited oral presentation
[Invited], [Domestic Conference]

Asymmetric Hydrogenation and Isomerization Catalyzed byChiral Ruthenium Complexes　　　　　　　　　　　　　　　
OHKUMA Takeshi
The 5th International Symposium on AMBITIOOUS LEASR'S PROGRAM, 21 Nov. 2017, English, Invited oral presentation
[Invited], [International presentation]

Asymmetric Hydrogenation and Isomerization with Chiral Ru(II) Catalysts　　　　　　　　　　　　　　　
OHKUMA Takeshi
5th UK-Japanese Symposium on Asymmetric Catalysis, 15 Mar. 2016, English, Invited oral presentation
[Invited], [International presentation]

Enantioselective Cyanation Catalyzed by Ru Complex/Li Compound Combined Systems　　　　　　　　　　　　　　　
OHKUMA Takeshi
The 6th Japanese-Sino Symposium on Organic Chemistry for Young Scientists, 07 Jul. 2015, English, Invited oral presentation
[Invited], [International presentation]

Asymmetric Hydrogenation and Isomerization Catalyzed by Ruthenium(II) Complexes　　　　　　　　　　　　　　　
OHKUMA Takeshi
8th Singapore International Chemistry Conference 2014, 16 Dec. 2014, English, Invited oral presentation
[Invited], [International presentation]

Enantioselective Hydrogenation and Isomerization with Chiral Ruthenium(II) Catalysts　　　　　　　　　　　　　　　
OHKUMA Takeshi
The 9th International Conference on Cutting-Edge Organic Chemistry in Asia, 02 Dec. 2014, English, Invited oral presentation
[Invited], [International presentation]

Asymmetric Hydrogenatin with Ruthenium Complexes　　　　　　　　　　　　　　　
OHKUMA Takeshi
日産化学学術講演会, 19 Nov. 2014, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

Asymmetric Hydrogenatin with Molecular Catalysts　　　　　　　　　　　　　　　
OHKUMA Takeshi
タワーホール船堀（東京都江戸川区）, 15 Oct. 2014, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

Preface/Opening Remarks　　　　　　　　　　　　　　　
OHKUMA Takeshi
Frontier Chemistry Center The 3rd International Symposium "Challenges at the Frontier of Chemical Sciences", 13 Jun. 2014, English, Invited oral presentation
[Invited], [International presentation]

Preface/Opening Remarks　　　　　　　　　　　　　　　
OHKUMA Takeshi
Frontier Chemistry Center The 2nd International Symposium "Advanced Material Science", 09 Dec. 2013, English, Invited oral presentation
[Invited], [International presentation]

Practical Synthesis of Optically Active Aicohols　　　　　　　　　　　　　　　
OHKUMA Takeshi
Inovation Japan 2013, 29 Aug. 2013, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

Kinetic Resolution of α-Hydroxy Esters Catalyzed by Chiral Cu Complexes　　　　　　　　　　　　　　　
OHKUMA Takeshi
JST Symposium, 11 Mar. 2013, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

Preface/Opening Remarks　　　　　　　　　　　　　　　
OHKUMA Takeshi
Frontier Chemistry Center The 1st International Symposium "Next Generation of Molecular Chemistry", 22 Feb. 2013, English, Invited oral presentation
[Invited], [International presentation]

Asymmetric Hydrogenation for Practical Synthesis of Chiral Molecules　　　　　　　　　　　　　　　
OHKUMA Takeshi
The 4th Symposium on Academic Exchange and Collaborative Research between MRC-ETHZ and FoE-HU (Coorganized by Frontier Chemistry Center of FoE-HU), 21 Feb. 2013, English, Invited oral presentation
[Invited], [International presentation]

Asymmetric Hydrogenation of Ketones and Imines Catalyzed by Ru(II) Complexes　　　　　　　　　　　　　　　
OHKUMA Takeshi
2012 Hokkaido University & Peking University Joint Symposium on Organic and Organometallic Chemistry, 17 Jul. 2012, English, Invited oral presentation
[Invited], [International presentation]

Asymmetric Cyanation Catalyzed by Ru-Li Combined Systems　　　　　　　　　　　　　　　
OHKUMA Takeshi
The 5th GCOE International Symposium/The 1st International Symposium of Graduate School of Chemical Sciences and Engineering, 21 Feb. 2012, English, Invited oral presentation
[Invited], [International presentation]

Asymmetric Cyanation Catalyzed by the Chiral Ru-Li Combined Systems　　　　　　　　　　　　　　　
OHKUMA Takeshi
大阪大学基礎工学研究科学術講演会, 02 Dec. 2011, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

Asymmetric Cyanosilylation of Aldehydes and α-Keto Esters with the Chiral Ru–Li Combined Catalysts　　　　　　　　　　　　　　　
OHKUMA Takeshi
Joint Pre-Symposium on Organometallic Chemistry, 18 Jul. 2010, English, Invited oral presentation
[Invited], [International presentation]

Asymmetric Cyanosilylation of Aldehydes and α-Keto Esters Catalyzed by the Chiral Ru–Li Combined Systems　　　　　　　　　　　　　　　
OHKUMA Takeshi
22nd International Symposium on Chirality 2010, 15 Jul. 2010, English, Invited oral presentation
[Invited], [International presentation]

Asymmetric Hydrogenation of Ketones Catalyzed by Chiral Ru(II) Complexes　　　　　　　　　　　　　　　
OHKUMA Takeshi
BIT's 1st Annual World Congress of Catalytic Asymmetric Synthesis-2010, 20 May 2010, English, Invited oral presentation
[Invited], [International presentation]

Practcal Synthesis of Optically Active Amino Alcohols　　　　　　　　　　　　　　　
OHKUMA Takeshi
ファーマ i ジャパン, 02 Jul. 2009, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

Asymmetric Reduction of Unsaturated Compounds　　　　　　　　　　　　　　　
OHKUMA Takeshi
有機合成化学講習会, 18 Jun. 2009, Japanese, Public discourse
[Invited], [Domestic Conference]

Asymmetric Cyanosilylation of Aldehydes with the Chiral Ru–Li Catalyst System　　　　　　　　　　　　　　　
OHKUMA Takeshi
The 4th Hokkaido University–Nanjing University Joint Symposium, 17 Dec. 2008, English, Invited oral presentation
[Invited], [International presentation]

Asymmetric Cyanosilylation of Aldehydes with Chiral Ruthenium Catalysts　　　　　　　　　　　　　　　
OHKUMA Takeshi
Taiwan-Japan International Symposium on Organic Chemistry and Molecular Science, 18 Apr. 2008, English, Invited oral presentation
[Invited], [International presentation]

Tailor-made触媒を用いるケトン類の不斉水素化　　　　　　　　　　　　　　　
大熊 毅
近畿化学協会有機金属部会平成１９年度第３回例会, 22 Nov. 2007, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

Tailor-made触媒によるケトン類の不斉水素化　　　　　　　　　　　　　　　
大熊 毅
2007年度 大塚有機合成シンポジウム, 04 Oct. 2007, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

Asymmetric Hydrogenation of Ketones Catalyzed by Tailor-made Ruthenium(II) Complexes　　　　　　　　　　　　　　　
OHKUMA Takeshi
2nd International Conference on Cutting-Edge Organic Chemistry in Asia, 05 Sep. 2007, English, Invited oral presentation
[Invited], [International presentation]

Asymmetric Hydrogenation of Ketones Catalyzed by Tailot-made Ru complexes　　　　　　　　　　　　　　　
OHKUMA Takeshi
The 16th Symposium on Optically Active Compounds, 27 Oct. 2006, English, Invited oral presentation
[Invited], [International presentation]

Asymmetric Hydrogenation of tert-Alkyl Ketones and 1-Tetralones　　　　　　　　　　　　　　　
OHKUMA Takeshi
The 2005 International Chemical Congress of Pacific Basin Societies, 16 Dec. 2005, English, Invited oral presentation
[Invited], [International presentation]

Asymmetric Hydrogenation of Ketones -Design of Chiral Catalysts-　　　　　　　　　　　　　　　
OHKUMA Takeshi
The 15th International Symposium on Fine Chemistry and Functional Polymer (FCFPXIV-2005) & IUPAC 1st International Symposium on Novel Materials and Synthesis (NM-1), 18 Oct. 2005, English, Invited oral presentation
[Invited], [International presentation]

ルテニウム錯体触媒を用いるケトン類の不斉水素化　　　　　　　　　　　　　　　
大熊 毅
第４５回オーロラセミナー第２回規則性多孔体研究会合同セミナー, 25 Jul. 2005, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

ケトン類の不斉水素化ー分子世界の左と右ー　　　　　　　　　　　　　　　
大熊 毅
慶應義塾大学理工学部同窓会研究・教育奨励基金による特別講演会, 18 Jun. 2005, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

ケトン類の不斉水素化ー分子触媒を用いるアプローチー　　　　　　　　　　　　　　　
大熊 毅
第１回生体触媒化学若手講演会, 25 Mar. 2005, Japanese, Invited oral presentation
横浜, [Invited], [Domestic Conference]

Asymmetric Hydrogenation of Simple Ketones　　　　　　　　　　　　　　　
OHKUMA Takeshi
第１５回北海道大学触媒化学研究センター研究討論会, 12 Nov. 2004, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

Asymmetric Hydrogenation of Simple Ketones Catalyzed by Ruthenium Complexes　　　　　　　　　　　　　　　
OHKUMA Takeshi
The 14th International Symposium on Fine Chemistry and Functional Polymer (FCFP XIV-2004), 17 Aug. 2004, English, Invited oral presentation
[Invited], [International presentation]

新規ルテニウムヒドリド錯体触媒を用いるケトン類の不斉水素化　　　　　　　　　　　　　　　
大熊 毅
第３７回有機金属若手の会 夏の学校, 16 Jul. 2004, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

Asymmetric Hydrogenation of Ketones with Chiral Ru Complexes　　　　　　　　　　　　　　　
OHKUMA Takeshi
北海道大学大学院工学研究科 学術講演会, 03 Mar. 2004, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

Asymmetric Hydrogenation of Ketones　　　　　　　　　　　　　　　
OHKUMA Takeshi
日本化学会創立125周年記念 第15回名古屋コンファレンス「産官学連携と化学」, 18 Dec. 2003, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

Development of Efficient Molecular Catalysts　　　　　　　　　　　　　　　
OHKUMA Takeshi
21世紀COE形成プログラム「分子機能の解明と創造」：第１回成果報告会, 18 Jun. 2003, Japanese, Invited oral presentation
[Invited], [Domestic Conference]

２１世紀を担う機能性物質　　　　　　　　　　　　　　　
北海道大学一般教育演習

有機化学I　　　　　　　　　　　　　　　
北海道大学工学部応用化学コース

有機化学II　　　　　　　　　　　　　　　
北海道大学工学部応用化学コース

物質変換工学　　　　　　　　　　　　　　　
北海道大学応用理工系学科

先端の化学　　　　　　　　　　　　　　　
北海道大学全学教育

大学院集中講義　　　　　　　　　　　　　　　
大阪大学大学院基礎工学研究科

基礎有機化学　　　　　　　　　　　　　　　
北海道大学工学部応用化学コース

有機化学III　　　　　　　　　　　　　　　
北海道大学工学部応用化学コース

有機化学IV　　　　　　　　　　　　　　　
北海道大学工学部応用化学コース

有機反応論特論　　　　　　　　　　　　　　　
北海道大学大学院総合化学院

応用化学特別講義　　　　　　　　　　　　　　　
北海道大学大学院総合化学院

有機反応構造論　　　　　　　　　　　　　　　
北海道大学大学院総合化学院

有機化学特論　　　　　　　　　　　　　　　
北海道大学大学院総合化学院

有機反応・構造論　　　　　　　　　　　　　　　
北海道大学大学院総合化学院

Published paper was introduced on the Organic Chemistry Portal https://www.organic-chemistry.org/abstracts/lit7/974.shtm　　　　　　　　　　　　　　　
H. Ece, Y. Tange, T. Yurino, T. Ohkuma, 01 Apr. 2022 - Present

Citations for Chemical Breakthrough Awards (2021) (American Chemical Society)　　　　　　　　　　　　　　　
R. Noyori, T. Ohkuma, M. Kitamura, Nagoya University, H. Takaya, Molecular Science, N. Sayo, H. Kumabayashi, S. Akutagawa, Takasago International Corperation, 20 Jan. 2022 - Present

Topic Information　　　　　　　　　　　　　　　
関東化学株式会社, 01 Apr. 2021 - Present

新聞掲載（複数社）される「アジアで初の米国化学会「歴史的化学論文大賞」を受賞」　　　　　　　　　　　　　　　
R. Noyori, T. Ohkuma, M. Kitamura, Nagoya University, H. Takaya, Molecular Science, N. Sayo, H. Kumabayashi, S. Akutagawa, Takasago International Corperation, 20 Jan. 2022 - 20 Jan. 2022

化学工業日報記事掲載「不斉水素化触媒を新開発 医薬品向け受託合成も活況」
21 Jun. 2020 - 21 Jun. 2020, 13483696

Commercialization of Catalysts for Asymmetric Hydrogenation: s-PICA　　　　　　　　　　　　　　　
Takeshi Ohkuma, Dec. 2019, [Others]

北海道大学研究シーズ集Vol. 4 (2017) 掲載「均一系パラジウムナノ粒子触媒による水素化反応 —シスアルケンとアミン類の選択的合成—」 ナノテク・材料分野 p100　　　　　　　　　　　　　　　
大熊 毅, 2017, [Others]

不斉シアノ化触媒市販開始（日本曹達・関東化学）カタログ作成「—不斉シアノ化触媒—Catalyst for Asymmetric Hydrocyanaiton Asymmetric Cyanosilylation」　　　　　　　　　　　　　　　
大熊 毅, 2017, [Others]

The Chemical Recordの”Special Issue Dedicted to Professor Ryoji Noyori on the 15th Anniversary of His Nobel Prize in Chemistry”でGuest Editorを務めた　　　　　　　　　　　　　　　
大熊 毅, Dec. 2016, [Others]

北海道大学研究シーズ集Vol. 3 (2016) 掲載「アリルアルコール類の不斉異性化反応 —光学活性β-置換アルデヒド類の高純度合成法—」 ナノテク・材料分野 p99　　　　　　　　　　　　　　　
大熊 毅, 2016, [Others]

北海道大学研究シーズ集Vol. 2 (2015) 掲載「カルボニル化合物、イミン類の不斉シアノ化反応 —ルテニウム・リチウム複合錯体触媒による多様な光学活性シアン化物の合成—」　　　　　　　　　　　　　　　
大熊 毅, Jun. 2015, [Others]

CSJ Journal Selects Vol. 2 掲載“Preparation of Diastereomerically Pure and Mixed (S)-PhGly/BIPHEP/Ru(II) Complexes and Their Catalytic Behavior with Li2O3 in Asymmetric Cyanosilylation of Benzaldehyde” Asymmetric Catalysis 分野 p5　　　　　　　　　　　　　　　
大熊 毅, 2015, [Others]

Symposium Organizer "Frontier Chemistry Center The 3rd International Symposium" "Challenges at the Frontier of Chemical Sciences"　　　　　　　　　　　　　　　
OHKUMA Takeshi, Jun. 2014, [Others]

北海道大学研究シーズ集2014掲載「ケトン類・イミン類の不斉水素化反応 —ルテニウム錯体触媒による光学活性アルコール類・アミン類の実用的合成法—」　　　　　　　　　　　　　　　
大熊 毅, May 2014, [Others]

学術雑誌に記事掲載 Editer’s Eye「光学活性アルデヒドの効率的な合成触媒を開発」「ファルマシア」　　　　　　　　　　　　　　　
大熊 毅, Dec. 2013, [Others]

新聞記事掲載「みんなでサイエンス 同じ分子に異なる性質？ 作り分けの技術を開発」「北海道新聞」　　　　　　　　　　　　　　　
大熊 毅, Dec. 2013, [Others]

Symposium Organizer "Frontier Chemistry Center The 2nd International Symposium" "Advanced Materials Science"　　　　　　　　　　　　　　　
OHKUMA Takeshi, Dec. 2013, [Others]

新聞記事掲載「受託製造ビジネス拡大 独自の触媒と配位子活用」「化学工業日報」　　　　　　　　　　　　　　　
大熊 毅, Nov. 2013, [Others]

新聞記事掲載「アルデヒド、１回で合成 北海道大 新触媒で純度９９％超」「日経産業新聞」　　　　　　　　　　　　　　　
大熊 毅, Jul. 2013, [Others]

発表論文が雑誌内表紙にハイライトされる　　　　　　　　　　　　　　　
大熊 毅, Jun. 2013, [Others]

Symposium Organizer "Frontier Chemistry Center The 1st International Symposium" "Next Generation of Molecular Chemistry"　　　　　　　　　　　　　　　
OHKUMA Takeshi, Feb. 2013, [Others]

Symposium Organizer "2012 Hokkaido University & Peking University Joint Symposium on Organic and Organometallic Chemistry"　　　　　　　　　　　　　　　
OHKUMA Takeshi, Jul. 2012, [Others]

シンポジウムオーガナイザー「北海道大学グローバルCOEシンポジウム 第１７回精密合成化学セミナー ジョイントシンポジウム」「分子変換と機能開発の新基軸」　　　　　　　　　　　　　　　
大熊 毅, Oct. 2011, [Others]

シンポジウムオーガナイザー「第２３回万有札幌シンポジウム」「有機化学の深化と多様化」　　　　　　　　　　　　　　　
大熊 毅, Jul. 2011, [Others]

新聞記事掲載「超高速の不斉水素化触媒」「化学工業日報」　　　　　　　　　　　　　　　
Jun. 2011, [Others]

シンポジウムオーガナイザー「第１６回精密合成化学セミナー」　　　　　　　　　　　　　　　
大熊 毅, Jan. 2011, [Others]

シンポジウムオーガナイザー「精密合成化学セミナー」「有機合成化学の新基軸」　　　　　　　　　　　　　　　
大熊 毅, Jan. 2009, [Others]

シンポジウムオーガナイザー「北海道大学グローバルCOEシンポジウム」「触媒的不斉合成の最先端」　　　　　　　　　　　　　　　
大熊 毅, Oct. 2008, [Others]

北海道大学大学院工学研究科公開講座「応用理工学研究の最先端〜豊かな生活を 目指して〜」「分子の世界の右手と左手」　　　　　　　　　　　　　　　
Oct. 2007, [Others]

日本化学会・ディビジョンレポート執筆　　　　　　　　　　　　　　　
2007

イノベーション・ジャパン２００７-大学見本市　　　　　　　　　　　　　　　
2007

夢・化学−２１「北海道大学化学系への二日間体験入学」　　　　　　　　　　　　　　　
2007

新聞記事掲載　　　　　　　　　　　　　　　
2007

Division reports of Japan Chemical Society　　　　　　　　　　　　　　　
2007

Inovation Japan 2007　　　　　　　　　　　　　　　
2007

「不斉還元」, 日本化学会　　　　　　　　　　　　　　　
2004 - 2006

新聞記事掲載　　　　　　　　　　　　　　　
2005

「Chirality in the Molecular World」　　　　　　　　　　　　　　　
2004

Development of Asymmetric Hydrogenation and Cyanation Catalyzed by Unique Ruthenium Complexes
科学研究費助成事業
Apr. 2024 - Mar. 2027
Takeshi Ohkuma
Japan Society for Promotion of Science, 基盤研究(C), Hokkaido University, Principal investigator, 24K08403

Development of Catalytic Organic Reactions Based on the Dynamic Behaviors of Molecules
Kakenhi (B)
Apr. 2019 - Mar. 2022
Takeshi Ohkuma
Japan Society for the Promotion of Science, Principal investigator, Competitive research funding

特異な配位子効果に基づく高機能金属錯体触媒の開拓　　　　　　　　　　　　　　　
科学研究費補助金(基盤研究(B))
2015 - 2017
大熊 毅
日本学術振興会, Principal investigator, Competitive research funding

Strategic Molecular and Materials Chemistry through Innovative Coupling Reactions　　　　　　　　　　　　　　　
文部科学省特別経費 大学の特性を生かした学術研究機能の充実
Apr. 2012 - Mar. 2016
OHKUMA Takeshi
Ministry of Education, Culture, Sports, Science, and Technology, Japan, Principal investigator, Competitive research funding

Overseas Visit Program for Young Prospective Researchers Involved in Innovative Chemistry for Efficient Molecular Conversion and the Creation of New Functional Materials　　　　　　　　　　　　　　　
Strategic Young Researcher Overseas Visits Program for Accelerating Brain Circulation
Oct. 2012 - Mar. 2015
OHKUMA Takeshi
Japan Society for the Promotion of Science, Principal investigator, Competitive research funding

Asymmetric Cyanation and Hydrogenation Catalyzed by Ruthenium Complexes
Grants-in-Aid for Scientific Research
2012 - 2014
OHKUMA Takeshi
Chiral Ru-Li combined systems developed by our research group efficiently catalyzed 1) hydrocyanation of aldehydes and N-protected aldimines, 2) cyanosilylation of simple and α-alkoxy ketones, and 3) conjugate hydrocyanation of α,β-unsaturated ketones and N-acylpyrroles. The substrate-to-catalyst molar ratio of 10,000 and enantioselectivity of 99% were achieved in the best cases.
The novel chiral Ru complexes achieved 1) very rapid and highly enantioselective hydrogenation of ketones, 2) asymmetric hydrogenation of N-arylimines, quinoxalines, and benzoxazines. The rate (turnover frequency) of the hydrogenation of ketones reached about 35,000 per minute with grater than 99% enantioselectivity. The turnover number of 18,000 and enantioselectivity of 99% in the reaction of N-arylimines were obtained in the best cases.
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (B), Hokkaido University, Principal investigator, Competitive research funding, 24350042

医薬合成重要原料「光学活性プロパルギルアルコール類」の高純度合成　　　　　　　　　　　　　　　
研究成果最適展開支援プログラム(A-STEP)(フィージビリティスタディ（探索タイプ））
Nov. 2012 - Oct. 2013
大熊 毅
科学技術振興機構, Principal investigator, Competitive research funding

重要医薬原料「光学活性α-ヒドロキシラクトン類・エステル類」の高純度合成　　　　　　　　　　　　　　　
研究成果最適展開支援プログラム(A-STEP)(フィージビリティスタディ（探索タイプ））
Aug. 2011 - Mar. 2012
大熊 毅
科学技術振興機構, Principal investigator, Competitive research funding

医薬等合成原料アルケン類の高効率合成法の開発　　　　　　　　　　　　　　　
研究成果最適展開支援プログラム(A-STEP)(フィージビリティスタディ（探索タイプ））
Oct. 2010 - Mar. 2011
大熊 毅
科学技術振興機構, Principal investigator, Competitive research funding

Asymmetric Reactions Catalyzed by Metal Complexes with two Chiral Ligands
Grants-in-Aid for Scientific Research
2009 - 2011
OHKUMA Takeshi
Chiral Ru(II) and Ir(III) complexes developped by our research groupi efficiently catalyzed 1) asymmetric cyanosilylation of aldehydes and ketones, 2) asymmetric hydrogenation of ketones, and 3) asymmetric 1,3-hydride migration of allylic alcohols : 1) Enantioselectivity as high as 99% in the reaction with a substrate-to-catalyst molar ratio (S/C) of 10,000 was achieved. 2) A series of chiral alcohols which is hardly prepared by the other methods was readily synthesized in high enantioselectivity. One of these ractions has been commercialized in the synthetic process of a chiral medicine. 3) The highest enantioselectivity of 98% in the reaction with an S/C of 1000 was achieved
Japan Society for the Promotion of Science, Grant-in-Aid for Scientific Research (B), Hokkaido University, Principal investigator, Competitive research funding, 21350048

医薬合成重要中間体「光学活性シアン化物」の高純度合成法の開発　　　　　　　　　　　　　　　
平成２１年度シーズ発掘試験（発展型）
Aug. 2009 - Mar. 2010
大熊 毅
科学技術振興機構, Principal investigator, Competitive research funding

医薬合成鍵中間体「光学活性アミノアルコール類」の高効率合成　　　　　　　　　　　　　　　
産学共同シーズイノベーション化事業 顕在化ステージ
Dec. 2008 - Nov. 2009
大熊 毅
科学技術振興機構, Principal investigator, Competitive research funding

医薬合成原料光学活性シアノヒドリンの高純度合成法の開発　　　　　　　　　　　　　　　
平成２０年度シーズ発掘試験（発掘型）
Jul. 2008 - Mar. 2009
大熊 毅
科学技術振興機構, Principal investigator, Competitive research funding

Asymmetric Hydrogenation of Ketones and Imines with Poly-Coordinated Chiral Catalysts
Grants-in-Aid for Scientific Research(基盤研究(B))
2006 - 2007
Takeshi OHKUMA
A series of ruthenium complexes with both chiral diphosphine and diamine ligands was designed and applied to asymmetric hydrogenation of ketones. The obtained results are described below1) Chiral 1,4-diamine IPHAN was prepared from mannitol. The TolBINAP/IPHAN-Ru complex effectively catalyzed asymmetric hydrogenation of 1-tetralones and their analogues in a base containing 2-propanol. The reaction was completed with a substrate-to-catalyst molar ratio (S/C) as high as 55,000 to afford the chiral alcohols in up to 99% enantiomeric excess (ee). Substituted 2-cyclohexenones were also converted...
Ministry of Education, Culture, Sports, Science and Technology, 基盤研究(B), 北海道大学, Principal investigator, Competitive research funding, 18350046

光学活性アルコール類の合成法の開発　　　　　　　　　　　　　　　
大学発事業創出研究開発事業
2004 - 2006
大熊 毅
新エネルギー・産業技術総合開発機構, Principal investigator, Competitive research funding

Exploitation of Fine Molecular Catalysts
Grants-in-Aid for Scientific Research(学術創成研究費)
2002 - 2006
Ryoji NOYORI, 大熊 毅, 斎藤 進, 伊丹 健一郎
(1) Asymmetric Hydrogenation of Ketones: Chiral RuC1_2(binap)(1, 2-diamine) complexes allow rapid, enantioselective hydrogenation of various simple, unfunctionalized ketones with a high substrate/catalyst molar ratio up to 2, 400, 000. As high practicality of this procedure became recognized, we have been encouraged to develop a robust (pre)catalyst that promotes the enantioselective reaction under base-free conditions. During the course of this program, we established that RuH(η^1-BH_4)(binap)(1, 2-diamine) complexes allow for asymmetric hydrogenation of simple ketones in 2-propanol withou...
Ministry of Education, Culture, Sports, Science and Technology, 学術創成研究費, 名古屋大学, Coinvestigator not use grants, Competitive research funding, 14GS0214

Mechanism of Asymmetric Hydrogenation of Ketones
Grants-in-Aid for Scientific Research(基盤研究(B))
2003 - 2004
Takeshi OHKUMA
Chiral diphosphine/1,2-diamine Ru(II) complexes catalyze the rapid, productive, and enantioselective hydrogenation of simple ketones. The reaction proceeds smoothly even at an atmospheric pressure of H_2 at room temperature and is further accelerated by addition of an alkaline base or a strong organic base. Most importantly, the hydrogenation rate is initially increased to a great extent with an increase in base molarity, but subsequently decreases. Without a base, the rate is independent on H_2 pressure in the range of 1-16 atm, while in the presence of a base, the reaction is accelerated ...
Ministry of Education, Culture, Sports, Science and Technology, 基盤研究(B), 名古屋大学->北海道大学, Principal investigator, Competitive research funding, 15350079

新規水素化触媒の開発　　　　　　　　　　　　　　　
産業技術実用化開発事業
2002 - 2004
大熊 毅
新エネルギー・産業技術総合開発機構, Principal investigator, Competitive research funding

金属ナノ粒子を用いる立体選択的水素化反応の開発　　　　　　　　　　　　　　　
基礎科学研究
2004
Competitive research funding

Development of Stereoselective Hydrogenation Catalyzed by Metal Nanoparticles　　　　　　　　　　　　　　　
Basic Science Research Program
2004
Competitive research funding

Asymmetric Hydrogenation of Ketones and Olefins
Grants-in-Aid for Scientific Research(基盤研究(B))
2001 - 2002
Takeshi OHKUMA
Homogeneous asymmetric catalysis provides a fundamental tool for the preparation of chiral building blocks for biologically important substances and advanced materials. Polymer-bound catalysts have inherent operational and economical advantages : immobilization on solid matrices facilitates the separation from reaction mixtures, recovery, and reuse of the expensive chiral compounds. Further, the solid-phase reaction offers a technical basis for diversity-oriented combinatorial synthesis. Numerous resin-supported (pre)catalysts have been developed along this line, though their practical appl...
Ministry of Education, Culture, Sports, Science and Technology, 基盤研究(B), 名古屋大学, Principal investigator, Competitive research funding, 13440188

生理機能を有する光学活性アルコール類の合成
科学研究費補助金(特定領域研究(A), 特定領域研究)
2001 - 2002
大熊 毅
本研究者の開拓した光学活性ジホスフィンとジアミンを配位子とするルテニウムジクロロ錯体は、アルカリ塩基の存在下、種々の芳香族およびα,β-不飽和ケトン類、アミノケトン類等の水素化に対して極めて高い触媒活性とエナンチオ選択性を示す。この塩化物錯体は、大気中でも安定なため操作性に優れているが、活性種を発生させるために強塩基の添加が不可欠である。したがって、塩基性条件下で不安定なケトン類の水素化には適用が困難であった。本研究では、塩基を添加せずに活性種を発生する触媒前駆体の探索研究を行った。塩化物錯体trans-RuCl_2[ (S)-xylbinap][ (S,S)-dpen](XylBINAP=2,2'-ビス(ジ-3,5-キシリルホスフィノ)-1,1'-ビナフチル、DPEN=1,2-ジフェニルエチレンジアミン)に水素化ホウ素ナトリウムを作用させることにより、ヒドリド錯体trans-RuH(η^1-BH_4)[ (S)-xylbinap][ (S,S)-dpen]を得た。この錯体は、塩基無添加条件でケトン類の水素化に対して極めて高い触媒活性とエナンチオ選択性を示した。例えば、アセトフェノンを10万分の1当量の錯体を用い、水素8気圧で水素化すると、反応は7時間で完結し、(R)-1-フェニルエタノールが99%の鏡像体過剰率で得られた。次に、塩基性条件下で容易に異性化するラセミ体α位置換シクロヘ...
文部科学省, 特定領域研究(A), 特定領域研究, 名古屋大学, Principal investigator, Competitive research funding, 13024239

Enantioselective Hydrogenation of Ketones
Grants-in-Aid for Scientific Research(基盤研究(B))
1999 - 2000
Takeshi OHKUMA
The development of practical methods effecting stereoselective hydrogenation of simple ketones is highly desirable, since the existing homogeneous catalysts lack reactivity and/or stereoselectivity. A new Ru (II) complex, trans-RuCl_2 [ (S)-xylbinap][ (S)-daipen] or the R, R enantiomer acts as an excellent precatalyst for asymmetric hydrogenation of simple ketones (XylBINAP=2, 2'-bis (di-3, 5-xylylphosphino)-1, 1'-binaphthyl. DAIPEN=1, 1-dianisyl-2-isopropyl-1, 2-ethylenediamine). The reaction is conducted with a substrate/catalyst molar ratio of up to 100000 in 2-propanol containing alkaline...
Ministry of Education, Culture, Sports, Science and Technology, 基盤研究(B), 名古屋大学, Principal investigator, Competitive research funding, 11440188

分子触媒を用いる不斉合成反応の開発　　　　　　　　　　　　　　　
基礎科学研究
1994
Competitive research funding

Development of Asymmetric Reactions with Molecular Catalysts　　　　　　　　　　　　　　　
Basic Science Research Program
1994
Competitive research funding

ケトン類の触媒的不斉水素化反応
科学研究費助成事業
1988 - 1989
大熊 毅
日本学術振興会, 奨励研究(A), 名古屋大学, 63790209

α-オキシニトリル、α-チオニトリル、α-アミノニトリル及びα-ホスファニトリルから選択されるニトリル化合物の製造方法　　　　　　　　　　　　　　　
Patent right, 百合野 大雅, 高島 拓也, 大熊 毅, 北海道大学
特願2023-033163, 03 Mar. 2023

Synthetic Method of Allylic Isocyanides
Patent right, Takeshi Ohkuma, Taiga Yurino, Hokkaido University; Nihonsoda
特願2017-35319, 27 Feb. 2017
特許第6871540号, 20 Apr. 2021
Hokkaido University; Nihonsoda
13483696

光学活性なヒドロキシエステル類またはヒドロキシアミド類の製造方法　　　　　　　　　　　　　　　
Patent right, 大熊 毅, 新井則義, 安田俊尚, 内海典之, 片山武昭, 国立大学法人北海道大学，関東化学株式会社
特願2020-174920, 16 Oct. 2020

光学活性２級アルコールの製造方法　　　　　　　　　　　　　　　
Patent right, 片山武昭, 堤 邦彦, 村田邦彦, 大熊 毅, 新井則義
特願2013-156036, 26 Jul. 2013
特開2015-24976, 05 Feb. 2015
特許第6437187号
22 Nov. 2018

光学活性２級アルコールの製造方法　　　　　　　　　　　　　　　
Patent right, 片山武昭, 堤 邦彦, 村田邦彦, 大熊 毅, 新井則義
特願2013-156016, 26 Jul. 2013
特開2015-24975, 05 Feb. 2015
特許第6291179号
16 Feb. 2018

光学活性アミン化合物の製造方法　　　　　　　　　　　　　　　
Patent right, 大熊 毅, 新井則義, 内海典之, 村田邦彦, 堤 邦彦
特願2013-017845, 31 Jan. 2013
特開2013-177374, 09 Sep. 2013
特許第6173702号
14 Jul. 2017

Synthetic Method of 3-Substituted 4-Chroman-4-ols　　　　　　　　　　　　　　　
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200903058028769630

光学活性アルコールおよびその誘導体の製造方法
Patent right, 野依 良治, 北村 雅人, 大熊 毅, 雲林 秀徳, 高砂香料工業株式会社
特願昭63-037032, 19 Feb. 1988
特開平1-211551, 24 Aug. 1989
201103077902736790

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