Updated on 2023/09/29

写真a

 
OHMATSU, Kohsuke
 
Organization
Institute of Transformative Bio-Molecules Designated associate professor
Graduate School
Graduate School of Engineering
Title
Designated associate professor
Contact information
メールアドレス

Degree 1

  1. Ph D. of Science ( 2008.3   Kyoto University ) 

Research Interests 1

  1. Catalytic Asymmetric Reactions, Organocatalysts, Organometallic Catalysts

Research Areas 2

  1. Others / Others  / Organic Chemistry

  2. Others / Others  / Synthetic Chemistry

Current Research Project and SDGs 1

  1. Development of Molecular Catalysts for Hitherto Difficult Chemical Transformation

Research History 2

  1. 名古屋大学大学院工学研究科化学・生物工学専攻 助教

    2008.4

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    Country:Japan

  2. JSPS Research Fellowship DC1

    2005.4 - 2008.3

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    Country:Japan

Education 3

  1. Kyoto University   Graduate School, Division of Natural Science   Department of Chemistry

    2005.4 - 2008.3

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    Country: Japan

  2. Kyoto University   Graduate School, Division of Natural Science   Department of Chemistry

    2003.4 - 2005.3

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    Country: Japan

  3. Kyoto University   Faculty of Science   Department of Chemistry

    1999.4 - 2003.3

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    Country: Japan

Professional Memberships 2

  1. The Chemical Society of Japan

  2. The Society of Synthetic Organic Chemistry, Japan

Awards 6

  1. Lectureship Award MBLA 2020

    2020  

  2. 文部科学大臣表彰 若手科学者賞

    2017  

  3. 日本化学会進歩賞

    2016   日本化学会  

    大松亨介

  4. Chemist Award BCA 2020

    2020  

  5. 若い世代の特別講演会講演証

    2014   日本化学会  

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    Country:Japan

  6. 赤崎賞

    2013   名古屋大学  

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    Country:Japan

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Papers 48

  1. Zwitterionic Diphenylphosphinyl Amidate as a Powerful Photoinduced Hydrogen-Atom-Transfer Catalyst for C-H Alkylation of Simple Alkanes

    Ohmatsu Kohsuke, Suzuki Ryuhei, Fujita Hiroki, Ooi Takashi

    JOURNAL OF ORGANIC CHEMISTRY   Vol. 88 ( 10 ) page: 6553 - 6556   2023.1

  2. Hydrogen-Atom Transfer Catalysis for C-H Alkylation of Benzylic Fluorides

    Ohmatsu Kohsuke, Suzuki Ryuhei, Fujita Hiroki, Ooi Takashi

    ORGANIC LETTERS   Vol. 24 ( 17 ) page: 3134 - 3137   2022.5

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  3. Thioamidate Ion as Effective Cocatalyst for Photoinduced C-H Alkylation via Multisite Proton-coupled Electron Transfer

    Ohmatsu Kohsuke, Fujimori Haruka, Minami Kodai, Nomura Kosuke, Kiyokawa Mari, Ooi Takashi

    CHEMISTRY LETTERS   Vol. 51 ( 4 ) page: 445 - 447   2022.4

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    Language:Japanese  

    DOI: 10.1246/cl.220026

    Web of Science

  4. Hydrogen-Atom-Transfer-Mediated Acceptorless Dehydrogenative Cross-Coupling Enabled by Multiple Catalytic Functions of Zwitterionic Triazolium Amidate

    Minami Kodai, Ohmatsu Kohsuke, Ooi Takashi

    ACS CATALYSIS   Vol. 12 ( 3 ) page: 1971 - 1976   2022.2

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    Language:Japanese  

    DOI: 10.1021/acscatal.1c05604

    Web of Science

  5. In Silico Analysis and Synthesis of Nafamostat Derivatives and Evaluation of Their Anti-SARS-CoV-2 Activity

    Fujimoto Kazuhiro J., Hobbs Daniel C. F., Umeda Miki, Nagata Akihiro, Yamaguchi Rie, Sato Yoshitaka, Sato Ayato, Ohmatsu Kohsuke, Ooi Takashi, Yanai Takeshi, Kimura Hiroshi, Murata Takayuki

    VIRUSES-BASEL   Vol. 14 ( 2 )   2022.2

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    Language:Japanese  

    DOI: 10.3390/v14020389

    Web of Science

  6. Catalytic Asymmetric Strecker Reaction of Ketoimines with Potassium Cyanide

    Ohmatsu Kohsuke, Morita Yusuke, Kiyokawa Mari, Hoshino Kimihiro, Ooi Takashi

    ASIAN JOURNAL OF ORGANIC CHEMISTRY   Vol. 10 ( 12 ) page: 3237 - 3240   2021.12

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    Language:Japanese  

    DOI: 10.1002/ajoc.202100608

    Web of Science

  7. Catalytic Asymmetric Cyanoalkylation of Electron-Deficient Olefins with Potassium Cyanide and Alkyl Halides

    Ohmatsu Kohsuke, Morita Yusuke, Kiyokawa Mari, Ooi Takashi

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 143 ( 29 ) page: 11218 - 11224   2021.7

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    Language:Japanese  

    DOI: 10.1021/jacs.1c05380

    Web of Science

  8. Exploiting Transient Radical Cations as Bronsted Acids for Allylic C-H Heteroarylation of Enol Silyl Ethers

    Nakashima Tsubasa, Fujimori Haruka, Ohmatsu Kohsuke, Ooi Takashi

    CHEMISTRY-A EUROPEAN JOURNAL   Vol. 27 ( 36 ) page: 9253 - 9256   2021.6

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    Language:Japanese  

    DOI: 10.1002/chem.202101352

    Web of Science

  9. Mannich-type allylic C-H functionalization of enol silyl ethers under photoredox-thiol hybrid catalysis

    Nakashima Tsubasa, Ohmatsu Kohsuke, Ooi Takashi

    ORGANIC & BIOMOLECULAR CHEMISTRY   Vol. 19 ( 1 )   2021.1

  10. HYBRID CATALYSIS OF 8-QUINOLINECARBOXALDEHYDE AND BRONSTED ACID FOR EFFICIENT RACEMIZATION OF alpha-AMINO AMIDES AND ITS APPLICATION IN CHEMOENZYMATIC DYNAMIC KINETIC RESOLUTION

    Ohmatsu Kohsuke, Kiyokawa Mari, Shirai Yuto, Nagato Yuya, Ooi Takashi

    HETEROCYCLES   Vol. 103 ( 1 ) page: 218 - 224   2021

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    Language:Japanese  

    DOI: 10.3987/COM-20-S(K)32

    Web of Science

  11. Ion-paired Ligands for Palladium-catalyzed Allylic Alkylation under Base-free Conditions

    Ohmatsu Kohsuke, Matsuyama Naho, Nagato Yuya, Ooi Takashi

    CHEMISTRY LETTERS   Vol. 49 ( 9 ) page: 1114 - 1116   2020.9

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    DOI: 10.1246/cl.200264

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  12. Non-Enzymatic Hybrid Catalysis for Stereoconversion of l-Amino Acid Derivatives to d-Isomers

    Nagato Yuya, Kiyokawa Mari, Ueki Yusuke, Kikuchi Jun, Ohmatsu Kohsuke, Terada Masahiro, Ooi Takashi

    ASIAN JOURNAL OF ORGANIC CHEMISTRY   Vol. 9 ( 4 ) page: 561 - 565   2020.4

  13. Zwitterionic 1,2,3-Triazolium Amidate as a Catalyst for Photoinduced Hydrogen-Atom Transfer Radical Alkylation

    Ohmatsu Kohsuke, Suzuki Ryuhei, Furukawa Yukino, Sato Makoto, Ooi Takashi

    ACS CATALYSIS   Vol. 10 ( 4 ) page: 2627 - 2632   2020.2

  14. Cationic Organic Catalysts or Ligands in Concert with Metal Catalysts

    Ohmatsu Kohsuke, Ooi Takashi

    TOPICS IN CURRENT CHEMISTRY   Vol. 377 ( 6 )   2019.12

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1007/s41061-019-0256-1

    Web of Science

  15. Direct allylic C-H alkylation of enol silyl ethers enabled by photoredox-Bronsted base hybrid catalysis

    Ohmatsu Kohsuke, Nakashima Tsubasa, Sato Makoto, Ooi Takashi

    NATURE COMMUNICATIONS   Vol. 10   2019.6

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1038/s41467-019-10641-y

    Web of Science

  16. Organic Molecular Catalysts in Radical Chemistry: Challenges Toward Selective Transformations

    Uraguchi Daisuke, Ohmatsu Kohsuke, Ooi Takashi

    MOLECULAR TECHNOLOGY, VOL 4: SYNTHESIS INNOVATION     page: 163 - 197   2019

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  17. Protonated Bis-1,2,3-triazole as an Anion-Binding Chiral Bronsted Acid for Catalytic Asymmetric Friedel-Crafts Reaction of Indoles with Imines

    Furukawa Yukino, Suzuki Ryuhei, Nakashima Tsubasa, Gramage-Doria Rafael, Ohmatsu Kohsuke, Ooi Takashi

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   Vol. 91 ( 8 ) page: 1252-1257   2018.8

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1246/bcsj.20180098

    Web of Science

  18. Diastereo- and enantioselective phase-transfer alkylation of 3-substituted oxindoles with racemic secondary alkyl halides

    Ohmatsu Kohsuke, Furukawa Yukino, Kiyokawa Mari, Ooi Takashi

    CHEMICAL COMMUNICATIONS   Vol. 53 ( 98 ) page: 13113-13116   2017.12

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/c7cc07122a

    Web of Science

  19. Determination of the absolute configuration of compounds bearing chiral quaternary carbon centers using the crystalline sponge method

    Sairenji Shiho, Kikuchi Takashi, Abozeid Mohamed Ahmed, Takizawa Shinobu, Sasai Hiroaki, Ando Yuichiro, Ohmatsu Kohsuke, Ooi Takashi, Fujita Makoto

    CHEMICAL SCIENCE   Vol. 8 ( 7 ) page: 5132-5136   2017.7

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/c7sc01524k

    Web of Science

  20. In Situ Electrophilic Activation of Hydrogen Peroxide for Catalytic Asymmetric alpha-Hydroxylation of 3-Substituted Oxindoles

    Ohmatsu Kohsuke, Ando Yuichiro, Ooi Takashi

    SYNLETT   Vol. 28 ( 11 ) page: 1291-1294   2017.7

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1055/s-0036-1558958

    Web of Science

  21. A Modular Strategy for the Direct Catalytic Asymmetric α-Amination of Carbonyl Compound Reviewed

    Kohsuke Ohmatsu, Yuichiro Ando, Tsubasa Nakashima, Takashi Ooi

    Chem   Vol. 1 ( 5 ) page: 802-810   2016.11

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1016/j.chempr.2016.10.012

  22. Multiple Absolute Stereocontrol in Pd-Catalyzed [3+2] Cycloaddition of Oxazolidinones and Trisubstituted Alkenes Using Chiral Ammonium-Phosphine Hybrid Ligands Reviewed

    Naomichi Imagawa, Yuya Nagato, Kohsuke Ohmatsu, Takashi Ooi

    Bulletin of the Chemical Society of Japan   Vol. 89 ( 6 ) page: 649-656   2016

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1246/bcsj.20160053

  23. Anion Stoichiometry-Dependent Selectivity Enhancement in Ion-Paired Chiral Ligand/Pd Complex-Catalyzed Enantioselective Allylic Alkylation Invited Reviewed

    Kohsuke Ohmatsu, Yoshiyuki Hara, Yuya Kusano, Takashi Ooi

    Synlett   Vol. 27 ( 7 ) page: 1047-1050   2016

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1055/s-0035-1561403

  24. Palladium-Catalyzed Branch-Selective Decarboxylative Allylation Using Ion-Paired Ligands Reviewed

    Yoshiyuki Hara, Yuya Kusano, Kohsuke Ohmatsu, Takashi Ooi

    Chemistry Letters   Vol. 45 ( 5 ) page: 552-554   2016

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1246/cl.160158

  25. Catalytic Asymmetric Cyanation of Alkylideneindolenines Generated from Sulfonylalkylindoles

    Kohsuke Ohmatsu, Yukino Furukawa, Daigo Nakaguro, Takashi Ooi

    Chem. Lett.   Vol. 44 ( 10 ) page: 1350-1352   2015

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    DOI: 10.1246/cl.150581

  26. イオン対の活用に基づく新奇なキラル配位子の創製と応用

    大松亨介,大井貴史

    有機合成化学協会誌   Vol. 73 ( 2 ) page: 140-150   2015

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  27. Design of supramolecular chiral ligands for asymmetric metal catalysis

    Kohsuke Ohmatsu, Takashi Ooi

    Tetrahedron Lett.   Vol. 56   page: 2043-2048   2015

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    DOI: 10.1016/j.tetlet.2015.02.096

  28. Ligand-enabled multiple absolute stereocontrol in metal-catalysed cycloaddition for construction of contiguous all-carbon quaternary stereocentres Reviewed

    Kohsuke Ohmatsu, Naomichi Imagawa, Takashi Ooi

    Nature Chemistry   Vol. 6 ( 1 ) page: 47-51.   2014

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1038/NCHEM.1796

  29. Asymmetric Alkylation of α-Cyanosulfones Catalyzed by Chiral 1,2,3-Triazolium Salts Invited Reviewed

    Kohsuke Ohmatsu, Yusuke Hakamata, Ayano Goto, Takashi Ooi

    Heterocycles   Vol. 88 ( 2 ) page: 1661-1666   2014

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.3987/COM-13-S(S)121

  30. In-Situ Generation of Ion-Paired Chiral Ligands: Rapid Identification of Optimal Ligand for Palladium-Catalyzed Asymmetric Allylation Reviewed

    Kohsuke Ohmatsu, Yoshiyuki Hara, Takashi Ooi

    Chemical Science   Vol. 5 ( 9 ) page: 3645-3650   2014

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    Authorship:Lead author   Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/C4SC01032A

  31. Ligand-Controlled E/Z Selectivity and Enantioselectivity in Palladium-Catalyzed Allylation of Benzofuranones with 1,2-Disubstituted Allylic Carbonates Reviewed

    Kohsuke Ohmatsu, Mitsunori Ito, Takashi Ooi

    Chemical Communications   Vol. 10 ( 7 ) page: 4554-4557   2014

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    Authorship:Lead author   Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/C3CC49338E

  32. Palladium-Catalyzed Asymmetric [3+2] Cycloaddition of 5-Vinyloxazolidinones with Imines Using Chiral Ammonium-Phosphine Hybrid Ligand Reviewed

    Kohsuke Ohmatsu, Shinya Kawai, Naomichi Imagawa, Takashi Ooi

    ACS Catalysis   Vol. 4 ( 12 ) page: 4304-4306   2014

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/cs501369z

  33. Exploiting the Modularity of Ion-Paired Chiral Ligands for Palladium-Catalyzed Enantioselective Allylation of Benzofuran-2(3H)-ones Reviewed

    Kohsuke Ohmatsu, Mitsunori Ito, Tomoatsu Kunieda, Takashi Ooi

    Journal of the American Chemical Society   Vol. 135 ( 2 ) page: 590–593   2013.1

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/ja312125a

  34. Carbene Transfer from Triazolylidene Gold Complexes as a Potent Strategy for Inducing High Catalytic Activity Reviewed

    Daniel Canseco-Gonzalez, Ana Petronilho, Helge Mueller-Bunz, Kohsuke Ohmatsu, Takashi Ooi, Martin Albrecht

    Journal of the American Chemical Society   Vol. 135 ( 35 ) page: 13193-13203   2013

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    DOI: 10.1021/ja406999p

  35. Asymmetric Substitution at the Tetrasubstituted Chiral Carbon: Catalytic Ring-Opening Alkylation of Racemic 2,2-Disubstituted Aziridines with 3-Substituted Oxindoles

    Kohsuke Ohmatsu, Yuichiro Ando, Takashi Ooi

    J. Am. Chem. Soc.   Vol. 135 ( 50 ) page: 18706-18709.   2013

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/ja411647x

  36. Catalytic Asymmetric Mannich-Type Reactions of α-Cyano α-Sulfonyl Carbanions Invited Reviewed

    Kohsuke Ohmatsu, Ayano Goto, Takashi Ooi

    Chemical Communications     2012.6

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/C2CC32398B

  37. Catalytic Asymmetric Ring Openings of Meso and Terminal Aziridines with Halides Mediated by Chiral 1,2,3-Triazolium Silicates Reviewed

    Kohsuke Ohmatsu, Yuta Hamajima, Takashi Ooi

    Journal of the American Chemical Society   Vol. 21 ( 134 ) page: 8794-8797   2012.6

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/ja3028668

  38. Ion-Paired Chiral Ligands for Asymmetric Palladium Catalysis Reviewed

    Kohsuke Ohmatsu, Mitsunori Ito, Tomoatsu Kunieda, Takashi Ooi

    Nature Chemistry   Vol. 6 ( 4 ) page: 473-477   2012.6

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    Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1038/nchem.1311

  39. Chiral 1,2,3-Triazoliums as New Cationic Organic Catalysts with Anion-Recognition Ability: Application to Asymmetric Alkylation of Oxindoles Reviewed

    Kohsuke Ohmatsu, Mari Kiyokawa, Takashi Ooi

    Journal of the American Chemical Society   Vol. 133 ( 5 ) page: 1307-1309   2011.1

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    DOI: doi/abs/10.1021/ja1102844

  40. Al Lewis acid-catalyzed regiodivergent 1,2-rearrangement of α-siloxy aldehydes: scope and mechanism Reviewed

    Kohsuke Ohmatsu, Takayuki Tanaka, Takashi Ooi, and Keiji Maruoka

    Tetrahedron   Vol. 65 ( 36 ) page: 7516-7522   2009

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  41. *An “Anti-Baldwin" 3-Exo-Dig Cyclization: Preparation of Vinylidene Cyclopropanes from Electron-Poor Alkenes Reviewed

    Matthew J. Campbell, Patrick D. Pohlhaus, Geanna Min, Kohsuke Ohmatsu, Jeffrey S. Johnson

    Journal of the American Chemical Society   Vol. 130 ( 29 ) page: 9180-9181   2008.6

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    Stabilized carbanions undergo an uncommon 3-exodig cyclization onto propargyl halides through an SN2′ substitution. Propargyl iodides as electrophiles are necessary to achieve good yields (36-95%) for most substrates, although the usefulness of chlorides and bromides is documented. A variety of monocyclic and bicyclic vinylidene cyclopropanes can be prepared. These products are not available by standard carbene methodology.

  42. *Complete Switch of Migratory Aptitude in Aluminum-Catalyzed 1,2-Rearrangement of Differently α,α-Disubstituted α-Siloxy Aldehydes Reviewed

    Kohsuke Ohmatsu, Takayuki Tanaka, Takashi Ooi, Keiji Maruoka

    Angewandte Chemie International Edition   Vol. 47 ( 58 ) page: 5203-5206   2008.6

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    The regiodivergent 1,2-rearrangement of α-siloxy aldehydes bearing α-aryl and α-alkyl substituents into a-siloxy ketones has been realized by using different aluminum Lewis acid catalyst/solvent systems. The scope of this unprecedented protocol has been investigated
    with various substrates and clearly demonstrates its utility for the selective synthesis of two structural isomers from one substrate.

  43. Practical Stereoselective Synthesis of β-Branched α-Amino Acids through Efficient Kinetic Resolution in the Phase-Transfer-Catalyzed Asymmetric Alkylations Reviewed

    Takashi Ooi, Daisuke Kato, Koji Inamura, Kohsuke Ohmatsu, Keiji Maruoka

    Organic Letters   Vol. 9 ( 20 ) page: 3945-3948   2007.11

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    Phase-transfer-catalyzed alkylation of glycinate Schiff base with racemic secondary alkyl halides proceeded with excellent levels of syn- and enantioselectivities under the influence of chiral quaternary ammonium bromide and 18-crown-6. The alkylation product can be selectively converted to the corresponding anti isomer, allowing the preparation of all the stereoisomers of β-alkyl-α-amino acid derivatives, an extremely valuable chiral building block.

  44. *Catalytic Asymmetric Rearrangement of α,α-Disubstituted α-Siloxy Aldehydes to Optically Active Acyloins Using Axially Chiral Organoaluminum Lewis Acids Reviewed

    Takashi, Ooi, Kohsuke Ohmatsu, Keiji Maruoka

    Journal of the American Chemical Society   Vol. 129 ( 9 ) page: 2410-2411   2007.2

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    A catalytic asymmetric rearrangement of α,α-dialkyl-α-siloxy aldehydes has been developed based on the design of a stereochemically defined, axially chiral organoaluminum Lewis acid. The scope of this unprecedented stereoselective rearrangement has been investigated with representative substrates, in which impressive kinetic resolution of racemic, α,α-disubstituted α-siloxy aldehydes has also been achieved. These results clearly demonstrate the utility of the present approach for the catalytic enantioselective synthesis of various acyloins and tertiary α-hydroxy aldehydes not readily accessible by the previously known asymmetric methodologies.

  45. 4. Organoaluminum-mediated selective 1,2-rearrangement of γ,γ-disubstituted γ-amino α,β-unsaturated carbonyl compounds leading to unsymmetrically substituted pyrroles Reviewed

    Takashi Ooi, Kohsuke Ohmatsu, Hiroki Ishii, Akira Saito, Keiji Maruoka

    Tetrahedron Letters   Vol. 45 ( 51 ) page: 9315-9317   2004.11

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    γ,γ-Dialkyl-γ-amino-,β-unsaturated carbonyl compounds were found to undergo selective skeletal rearrangement under the influence of modified organoaluminum Lewis acid to give unsymmetrically substituted pyrroles through the rapid Paal–Knorr type cyclization upon acidic hydrolysis. This new structural reorganization of amino carbonyl compounds triggered by the 1,2-alkyl shift provides a unique entry to the synthesis of pyrroles, an important class of heterocycles with diverse biological activities.

  46. Meerwein-Ponndorf-Verley alkynylation of aldehydes: Essential modification of aluminum alkoxides for rate acceleration and asymmetric synthesis Reviewed

    Takashi Ooi, Tomoya Miura, Kohsuke Ohmatsu, Akira Saito, Keiji Maruoka

    Organic and Biomolecular Chemistry   Vol. 2 ( 22 ) page: 3312-3319   2004.11

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    A novel carbonyl alkynylation has been accomplished based on utilization of the Meerwein–Ponndorf–Verley (MPV) reaction system. The success of the MPV alkynylation crucially depends on the discovery of the remarkable ligand acceleration effect of 2,2-biphenol. For example, the alkynylation of chloral (2c) with the aluminium alkoxide 6(R = Ph), prepared in situ from Me3Al, 2,2-biphenol and 2-methyl-4-phenyl-3-butyn-2-ol (1a) as an alkynyl source, proceeded smoothly in CH2Cl2 at room temperature to give the desired propargyl alcohol 3ca in almost quantitative yield after 5 h stirring. The characteristic feature of this new transformation involving no metal alkynides can be visualized by the fact that the alkynyl group bearing keto carbonyl was transferred successfully to aldehyde carbonyl without any side reactions on keto carbonyl. Although the use of (S)-1,1-bi-2-naphthol and its simple analogues was found to be unsuitable for inducing asymmetry in this reaction, design of new chiral biphenols bearing a certain flexibility of the biphenyl axis led to satisfactory results in terms of enantioselectivity as well as reactivity.

  47. Efficient asymmetric catalysis of chiral organoaluminum complex for enantioselective ene reactions of aldehydes Reviewed

    Takashi Ooi, Kohsuke Ohmatsu, Daisuke Uraguchi, and Keiji Maruoka

    Tetrahedron Letters   Vol. 45 ( 23 ) page: 4481-4484   2004.4

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    Chiral organoaluminum complex 1 efficiently catalyzed the asymmetric hetero-ene reaction of commercially available 2-methoxypropene with aldehydes under mild conditions to give the corresponding β-hydroxymethyl ketones in good to excellent chemical yields with high enantiomeric excesses. The asymmetric catalysis of 1 was further applied to the carbonyl addition of methallylsilanes, where exclusive formation of the optically active allylic silanes was achieved.

  48. Isopropoxyaluminum 1,1'-biphenyl-2-oxy-2'-perfluorooctanesulfonamide as a catalyst for Tishchenko reaction Reviewed

    Takashi Ooi, Kohsuke Ohmatsu, Kouji Sasaki, Tomoya Miura, Keiji Maruoka

    Tetrahedron Letters   Vol. 44 ( 15 ) page: 3191-3193   2003.3

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    Isopropoxyaluminum 1,1′-biphenyl-2-oxy-2′-perfluorooctanesulfonamide has been evaluated as an aluminum-based catalyst for the Tishchenko reaction. This compound was found to exert high catalytic activity in the reaction with aliphatic aldehydes and also enabled smooth dimerization of enolizable aldehydes. This advantage was highlighted by the quantitative formation of ethyl acetate from acetaldehyde by the present system.

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Books 1

  1. Aluminum Alkoxides and Phenoxides, Aluminum Amides

    Kohsuke Ohmatsu, Takashi Ooi( Role: Joint author)

    Georg Thieme Verlag KG  2011  ( ISBN:9783131643216

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    Language:English

Presentations 16

  1. Design of Modular Chiral Ionic Catalysts for Asymmetric Reactions Invited International conference

    Kohsuke Ohmatsu

    Shibasaki Corokium 

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    Event date: 2016.9

    Language:English   Presentation type:Public lecture, seminar, tutorial, course, or other speech  

    Venue:Tokyo   Country:Japan  

  2. イオン対の特性を活かした不斉触媒の設計と機能創出 Invited

    大松 亨介

    東京農工大学若手講演会 

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    Event date: 2016.4

    Language:Japanese   Presentation type:Public lecture, seminar, tutorial, course, or other speech  

    Country:Japan  

  3. Design of Small Molecules for Chemistry and Biology Invited

    Kohsuke Ohmatsu

    The 2nd CSRS-ITbM Joint Workshop 

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    Event date: 2016.1

    Language:English   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  4. Chiral 1,2,3-Triazolium Salts for Catalytic Asymmetric Reactions Invited

    Kohsuke Ohmatsu

    Cutting-Edge of Organocatalysts at The 95th CSJ Annual Meeting 

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    Event date: 2015.3

    Language:English   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  5. Asymmetric Synthesis of Chiral Small Molecules Containing Contiguous All-Carbon Quaternary Stereocenters Invited

    Kohsuke Ohmatsu

    The 2nd International Symposium on Transformative Bio-Molesules 

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    Event date: 2014.5

    Language:English   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  6. 光学活性1,2,3-トリアゾリウム塩の創製と触媒的不斉合成への応用

    大松亨介

    有機分子触媒による未来型分子変換  第1回有機分子触媒 若手セミナー  

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    Event date: 2012.9

    Language:Japanese   Presentation type:Oral presentation (general)  

    Country:Japan  

  7. Chiral 1,2,3-Triazolium Salts for Catalytic Asymmetric Reactions International conference

    Kohsuke Ohmatsu

    The 1st Nagoya Symposium on Green Synthesis & Catalysis  

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    Event date: 2012.3

    Language:English   Presentation type:Oral presentation (general)  

    Country:Japan  

  8. α-シロキシアルデヒドの1,2-転位反応における位置選択性の逆転

    大松亨介、田中隆行、大井貴史、丸岡啓二

    日本化学会第88春季年会 

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    Event date: 2008.3

    Language:Japanese   Presentation type:Oral presentation (general)  

    Country:Japan  

  9. Aluminum-Catalyzed Selective 1,2-Rearrangement of alpha,alpha-Disubstituted alpha-Siloxy Aldehydes International conference

    14th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS14) 

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    Event date: 2007.8

    Language:English   Presentation type:Poster presentation  

    Country:Japan  

  10. Catalytic Asymmetric 1,2-Rearrangement of alpha,alpha-Disubstituted alpha-Siloxy Aldehydes with Designer Axially Chiral Organoaluminum Lewis Acids

    International Conference on Asymmetric Organocatalysis 

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    Event date: 2007.5

    Language:English   Presentation type:Poster presentation  

    Country:Japan  

  11. 光学活性有機アルミニウムルイス酸を用いる新規触媒的不斉1,2-転位反応の開発

    大松亨介、大井貴史、丸岡啓二

    日本化学会第87春季年会 

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    Event date: 2007.3

    Language:Japanese   Presentation type:Oral presentation (general)  

    Country:Japan  

  12. 光学活性有機アルミニウムルイス酸を用いる新規触媒的不斉1,2-転位反応の開発

    日本化学会第86春季年会 

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    Event date: 2006.3

    Language:Japanese   Presentation type:Oral presentation (general)  

    Country:Japan  

  13. Chiral Organoaluminum-Catalyzed 1,2-Rearrangement of alpha,alpha-Disubstituted alpha-Siloxy Aldehydes International conference

    The 2005 International Chemical Congress of Pacific Basin Societies (Pacifichem 2005) 

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    Event date: 2005.12

    Language:English   Presentation type:Poster presentation  

  14. 高活性アルミニウムルイス酸を用いたγ,γ-ジアルキル-γ-アミノ-α,β-不飽和カルボニル化合物の骨格転位反応

    大松亨介、大井貴史、丸岡啓二

    日本化学会第85春季年会 

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    Event date: 2005.3

    Language:Japanese   Presentation type:Oral presentation (general)  

    Country:Japan  

  15. 光学活性有機アルミニウム触媒を用いる不斉エン反応の開発

    大松亨介、浦口大輔、大井貴史、丸岡啓二

    日本化学会第84春季年会 

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    Event date: 2004.3

    Language:Japanese   Presentation type:Oral presentation (general)  

    Country:Japan  

  16. 新規Meerwein-Ponndorf-Verley-Oppenauer(MPVO)触媒のTishchenko反応への適用

    大松亨介、佐々木弘司、三浦智也、大井貴史、丸岡啓二

    日本化学会第83春季年会 

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    Event date: 2003.3

    Language:Japanese   Presentation type:Oral presentation (general)  

    Country:Japan  

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KAKENHI (Grants-in-Aid for Scientific Research) 5

  1. トリアゾリウムアミデートの機能追究による高難度位置選択的分子変換

    Grant number:21H01930  2021.4 - 2024.3

    科学研究費助成事業  基盤研究(B)

    大松 亨介

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    Authorship:Principal investigator 

    Grant amount:\17550000 ( Direct Cost: \13500000 、 Indirect Cost:\4050000 )

    本研究では、既存法では困難な末端C-H選択的官能基化反応の開拓を目的に、ラジカルの発生制御を担う新規触媒システムの開発を行う。特に、N-ホスフィニルトリアゾリウムアミデートを前駆体とするラジカルカチオン触媒の分子設計と反応位置制御を中心的課題とし、HATに対して活性なC-H結合を有する化合物を基質とした末端C-H選択的変換反応を実現する。構造修飾が容易というN-ホスフィニルトリアゾリウムアミデートの特長を活かし、活性中心周りの空間を効果的に遮蔽できる分子構造を合理的に設計する。また、触媒合成と機能評価を通して、位置選択的なC-H結合変換を実現する触媒分子設計のひとつの指導原理を確立する。
    双性イオン型トリアゾリウムアミデートの機能を多角的に追究すべく、研究を推進した。本研究計画の端緒であったN-ホスフィニルトリアゾリウムアミデートを用いた末端選択的C-Hアルキル化反応については、位置選択性が触媒構造に応答せず、選択性を向上させることが困難であることを示す結果を得た。そのため、より構造多様性に富むN-アシル型触媒を活用した触媒開発を行なった。
    また、トリアゾリウムアミデートの共役酸であるアミドトリアゾリウムが、一電子還元を起点として分子状水素を放出し、自身はトリアゾリウムアミデートとして再生するというユニークな特質を発見し、適切な光レドックス触媒と協働させることで、アクセプターレス脱水素型クロスカップリング反応を実現した。本法は、種々の炭化水素化合物とオレフィンとのC-H/C-Hクロスカップリングを効率的に進行させる。酸化剤や水素発生触媒、電極等を必要とせず、水素ガスの副生を伴いながら生成物が生じる。トリアゾリウムアミデートとイリジウム光レドックス触媒のみで触媒反応が成立するが、2,4,6-コリジンのようなピリジン類縁体を添加することで、反応効率が向上することを見い出している。水素発生のための遷移金属錯体や電極を介さずにプロトンを分子状水素として放出する触媒システムは新奇であり、今後、反応機構の解明や水素発生効率をさらに向上させる触媒分子の開発を行うことで、様々な脱水素型反応の開拓に展開できることが見込まれる。
    C-H切断の位置制御に関しては、当初有望視していたN-ホスフィニルトリアゾリウムアミデートによる目標達成が困難であることが判明したものの、N-アシル型トリアゾリウムアミデートの構造設計・開発が着実に進行している。また、共役酸のアミドトリアゾリウムの一電子還元を起点として、触媒再生と水素発生が可能という当初予想していなかった発見をもとに、アクセプターレス脱水素型クロスカップリング反応という合成化学的に高難度な反応を実現したことが、研究の新しい方向性を切り拓く契機となった。触媒的に切断したC-H結合の水素原子を水素ガスとして放出する水素原子移動ー脱水素触媒システムの適用性は広く、様々な未踏の分子変換の実現につなげられると考えている。
    嵩高い置換基を有するN-アシル型トリアゾリウムアミデートの開発を継続し、位置選択的C-Hアルキル化反応の実現を目指す。N-ピバロイル基のような嵩高い置換基を導入すると、C-H結合を切断する水素原子移動(HAT)が進行しづらくなることがこれまでの研究で判明しているが、励起光レドックス触媒とアミデートからHAT活性なアミジルラジカルが生じる一電子移動が可逆であることがHAT過程の効率が不十分である要因になっていることも明らかにしている。そこで、適切な光レドックス触媒の探索等によりHAT過程の活性種であるアミジルラジカルの濃度を上昇させることで、嵩高い置換基導入による反応効率の低下を改善する。
    並行して、アクセプターレス脱水素型クロスカップリング反応の開拓を推し進める。水素発生過程の効率向上がカップリング反応の触媒回転数の向上につながると想定されることから、その実現に資する分子を探索する。また、炭化水素化合物と様々なカップリングパートナーとの反応を試み、触媒システムの適用性を検証する。

  2. Photo-induced generation of highly acidic species for the development of C-C bond-forming reaction

    Grant number:18K19073  2018.6 - 2020.3

    Grant-in-Aid for Challenging Research (Exploratory)

    Ohmatsu Kohsuke

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    Authorship:Principal investigator 

    Grant amount:\6240000 ( Direct Cost: \4800000 、 Indirect Cost:\1440000 )

    We developed a strategy for the allylic C-H alkylation of enol silyl ethers and their derivatives, which relies heavily on the combined use of appropriate photoredox and Bronsted base catalysts for the generation of requisite allylic radicals while suppressing undesired desilylation process. Under the hybrid catalysis, a series of enol silyl ethers smoothly react with electron-deficient olefins to give the corresponding functionalized enol silyl ethers. This operationally simple protocol, in concert with the ready availability of enol silyl ethers and their conventional polar reactivity, provides rapid and reliable access to an array of complex carbonyl compounds and will find widespread use among practitioners of organic synthesis.

  3. Design and Application of Zwitterionic Triazolium Amidate as Hydrogen-Atom Transfer Catalyst

    Grant number:18H01972  2018.4 - 2021.3

    Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    Ohmatsu Kohsuke

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    Authorship:Principal investigator 

    Grant amount:\17550000 ( Direct Cost: \13500000 、 Indirect Cost:\4050000 )

    The catalysis for hydrogen-atom transfer (HAT) is a powerful tool for the direct conversion of inert C-H bonds to C-C bonds. We have designed a zwitterionic 1,2,3-triazolium amidate as an effective modular hydrogen-atom transfer catalyst for photoredox C-H functionalization. This zwitterionic amidate is stable yet amenable to single-electron oxidation for generating a highly reactive amidyl radical. By the combined use with an appropriate Ir-based visible-light photoredox catalyst, we have accomplished efficient catalytic C-H alkylation of a range of C-H nucleophiles. These results provide the new approach to the design of HAT catalysts, and we believe that the judicious exploitation of the structural modularity of zwitterionic amidates holds vast potential for the development of catalyst-controlled selective C-H functionalization methodologies.

  4. イオン対の活用にもとづく超分子キラル反応場の創出

    Grant number:16H01015  2016.4 - 2018.3

    新学術領域研究(研究領域提案型)

    大松 亨介

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    Authorship:Principal investigator 

    Grant amount:\5980000 ( Direct Cost: \4600000 、 Indirect Cost:\1380000 )

    1,2,3-トリアゾールを主骨格とするアニオン捕捉型キラル分子を創製し、アキラルな酸との会合体の触媒機能評価に取り組んだ。さらに、組み合わせる酸を変更することで触媒の酸性度を調節できるという特徴を活かした反応開発を行った。アニオン捕捉分子として、C2対称構造をもつビス(アミド-1,2,3-トリアゾール)を合成し、反応制御に適切な酸性度の調節が必要なNスルホニルイミンへのインドールの付加反応をモデルとして触媒の機能評価を行った。ビストリアゾールとTfOHの1:1混合物を触媒として反応を実施したところ、目的の付加体が中程度の収率とエナンチオ選択性で得られ、同時にインドールが2分子付加した副生成物が生じた。副生成物は酸による目的生成物からのスルホンアミドの脱離を起点として生じるため、この経路を抑制するためには、触媒の酸性度を弱めることが効果的であると考えた。実際、組み合わせるアキラルな酸を比較的酸性度の低いものに変更することで、期待通り副生成物の生成を抑えることに成功した。キラルビストリアゾールとアキラルな酸との会合挙動について調べるため、1H NMRを用いた滴定実験やJob Plotの作成を行ったところ、ビストリアゾールと酸は1:2の会合体を形成し得ることや、ビストリアゾールのアミドプロトンはアニオンとの水素結合に関与しないことが示唆された。さらに各種比較実験の結果から、1:1会合体がより高い選択性を与えることや、アミド基は反応の促進と立体制御に重要であることが明らかになった。以上の知見をもとに反応条件の最適化とアミド基上の置換基修飾を重点的に検討した結果、標的とする付加反応を高収率かつ高エナンチオ選択的に進行させることに成功し、新たに開発した超分子型キラル酸触媒の力量を明示した。
    29年度が最終年度であるため、記入しない。
    29年度が最終年度であるため、記入しない。

  5. 連続不斉四級炭素をもつ擬天然生理活性化合物の創製を指向した精密迅速合成

    2014.4 - 2017.3

    科学研究費補助金  基盤研究(C)

    大松 亨介

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    Authorship:Principal investigator 

    不斉四級炭素が連続した骨格を有する分子を完璧な立体選択性で合成することは、現在の触媒的不斉合成を駆使しても極めて困難である。そのため、連続不斉四級炭素をもつ複雑なキラル化合物群の機能(生理活性等)に関する研究は、依然として未開拓のままである。もし、これまで合成困難であったキラル骨格を簡単かつ短工程で構築する手法を開発できれば、医薬をはじめとする新機能性物質の探索研究は飛躍的に進展する。本研究では、申請者が独自に開発してきた高機能で多様性に富んだ不斉触媒群を武器に、この目標を実現する。とくに多連続不斉四級炭素骨格の効率的構築法を開発し、擬天然生理活性化合物群の精密迅速合成を達成する。

Industrial property rights 2

  1. 1,2,3-トリアゾリウム塩

    大井貴史,大松亨介

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    Application no:特願2010-229144  Date applied:2010.10

    Country of applicant:Domestic  

  2. ホスフィン複合配位子

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    Application no:特願2010- 55043  Date applied:2010.3

    Country of applicant:Domestic  

 

Teaching Experience (On-campus) 6

  1. 有機化学III

    2016

  2. 基礎化学実験

    2016

  3. 有機合成化学

    2016

  4. 基礎セミナーA

    2014

  5. 有機化学実験第2

    2011

  6. 有機化学実験第1

    2011

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