HIRASHITA Tsunehisa

写真a

Affiliation Department etc.

Department of Life Science and Applied Chemistry
Department of Life Science and Applied Chemistry

Title

Associate Professor

Mail Address

E-mail address

Research Fields, Keywords

-

Graduate School

  •  
    -
    1999.03

    Nagoya Institute of Technology  Graduate School, Division of Engineering  Doctor's Course  Completed

Degree

  • Nagoya Institute of Technology -  Master (Engineering)

  • Nagoya Institute of Technology -  Doctor (Engineering)

Field of expertise (Grants-in-aid for Scientific Research classification)

  • Organic chemistry

  • Synthetic chemistry

 

Research Career

  • Organic Synthesis by Using Organometallic Compounds

    Collaboration in Organization   (not selected)  

    Project Year:  2002.04  -  Now

Papers

  • Reactions between 5-Nitroso-1,3-diphenyltetrazolium Salts and Electron-rich Arenes,

    Matsukawa, Yuta; Hirashita, Tsunehisa; Araki, Shuki

    Bulletin of the Chemical Society of Japan   92   540 - 544   2019.01  [Refereed]

    Research paper (scientific journal)   Multiple Authorship

    A series of reactions between 5-nitroso-1,3-diphenyltetrazolium tetrafluoroborate and methoxybenzenes, amines, thiols, sulfoxides, and sulfides, most of which are generally accepted asbeing inert to nitroso groups, is reported here. The tetrazoliumactivated nitroso functionality is capable of oxidizing the aforementioned substrates to give the corresponding oxidized products, and the nitroso tetrazolium itself is transformed into the corresponding amide or hydroxyamide, depending on the nature of the reaction partners. In the case of thioanisole, an addition product was obtained.

  • Copper(I)- and Mesoionic-Hydroxyamide-Catalyzed Chemoselective Aerobic Oxidation of Primary Benzylic Alcohols

    Matsukawa, Yuta; Hirashita, Tsunehisa

    Synlett   30   315 - 318   2019.01  [Refereed]

    Research paper (scientific journal)   Multiple Authorship

    A new aerobic oxidation system consisting of Cu(I)I, 2,2'-bipyridine, N-methyl imidazole, and a mesoionic hydroxyamide was developed, with which selective oxidation of a broad range of benzylic alcohols was achieved.

  • Revisiting Sodium Hypochlorite Pentahydrate (NaOCl·5H2O) for the Oxidation of Alcohols in Acetonitrile without Nitroxyl Radicals

    Tsunehisa Hirashita, Yuto Sugihara, Shota Ishikawa, Yohei Naito, Yuta Matsukawa,Shuki Araki

    Synlett   29   2404 - 2407   2018.10  [Refereed]

    Research paper (scientific journal)   Multiple Authorship

    Sodium hypochlorite pentahydrate (NaOCl·5H2O) is capable of oxidizing alcohols in acetonitrile at 20 °C without the use of catalysts. The oxidation is selective to allylic, benzylic, and secondary alcohols. ­Aliphatic primary alcohols are not oxidized.

  • Indium-Mediated Allylation of Carbonyl Compounds in Ionic Liquids: Effect of Salts in Ionic Liquids

    Tsunehisa Hirashita, Fusako Takahashi, Takayuki Noda, Yuji Takagi, Shuki Araki

    Molecules     2018.07  [Refereed]  [Invited]

    Research paper (scientific journal)   Multiple Authorship

    The In-mediated allylation of carbonyl compounds can be performed in various types of solvents including ionic liquids. However, we have found that in [bmim][BF4] (where bmim = 1-butyl-3-methylimidazolium), the In-mediated coupling of crotyl bromide with benzaldehyde gives a complex mixture, and some additives, such as halides and amines, are crucial for the successful conversion to the corresponding γ-adduct. Instead, the addition of alcohols or water promotes the formation of the α-adduct. An asymmetric induction with up to 62% enantiomeric excess (ee) was observed employing cinchonidine as an additive in a binary solvent consisting of an ionic liquid and dichloromethane.

  • Nitrosotetrazolium-Catalyzed Aerobic Oxidation of Alcohols to the Corresponding Carbonyl Compounds

    Yuta Matsukawa, Tsunehisa Hirashita, Shuki Araki

    European Journal of Organic Chemistry     2018.02  [Refereed]

    Research paper (scientific journal)   Multiple Authorship



    A mesoionic‐nitrosotetrazolium‐catalyzed aerobic oxidation of alcohols is reported. In the presence of catalytic amounts of 5‐nitroso‐1,3‐diphenyltetrazolium tetrafluoroborate (5 mol‐%) and nitric acid (20 mol‐%), a wide range of alcohols are oxidized to the corresponding aldehydes and ketones in yields of 53–100 % at room temperature under ambient air or oxygen conditions. This oxidation shows a strong preference for secondary alcohols over primary alcohols; sterically hindered alcohols are also smoothly oxidized. A mechanism involving a nitroso/NOx catalytic cycle is proposed.

  • 5-Nitroso-1,3-diphenyltetrazolium salt as a mediator for the oxidation of alcohols

    Yuta Matsukawa, Tsunehisa Hirashita, Shuki Araki

    Tetrahdron ( Elsevier )  73 ( 42 ) 6052 - 6056   2017.10  [Refereed]

    Research paper (scientific journal)   Multiple Authorship

    We describe the synthesis of a mesoion-derived nitroso compound, 5-nitroso-1,3-diphenyltetrazolium tetrafluoroborate (1), and its application in the oxidation of alcohols. The structure of 1 was fully characterized by X-ray analysis, showing that it exists as a monomer in the solid state. In the cyclic voltammetric analysis of 1, a reversible redox peak was observed at 0.43 V (vs. Ag/Ag+ in MeCN) under acidic conditions. It was subsequently shown that the nitrosotetrazolium salt 1 is capable of stoichiometrically oxidizing alcohols to the corresponding carbonyl compounds effectively. This nitroso heterocycle and its reduced form, i.e., the corresponding mesoionic hydroxyamide, participate in a redox cycle involving the catalytic oxidation of alcohols by the aid of HNO3 under mild condition

  • Enantioselective Barbier-type allylation of ketones using allyl halide and indium in water

    Shuichi Nakamura, Yoshichika Hara, Takashi Furukawa,Tsunehisa Hirashitaa

    RSC Advances ( Royal Society of Chemistry )  7   15582 - 15585   2017.03  [Refereed]

    Research paper (scientific journal)   Multiple Authorship

  • Ionic TEMPO in Ionic Liquids: Specific Promotion of the Aerobic Oxidation of Alcohols

    Tsunehisa Hirashita,*[a] Makoto Nakanishi,[a] Tomoya Uchida,[a] Masakazu Yamamoto,[a]

    ChemCatChem   8   2704 - 2709   2016.08  [Refereed]

    Research paper (scientific journal)   Multiple Authorship

    The main objective of this study was to design a recyclable
    TEMPO (2,2,6,6-tetramethylpiperidinyl-N-oxyl) derivative that
    could be used as a catalyst in an ionic liquid solvent for the
    aerobic oxidation of alcohols by using NaNO2 and HCl as cocatalysts.
    To this end, a TEMPO derivative bearing a quaternary
    ammonium group, [4-Bu2MeN-TEMPO][PF6] (1), was prepared.
    It was subsequently shown that this ionic TEMPO derivative is
    an efficient catalyst for the aerobic oxidation of a variety of primary
    and secondary alcohols. It exhibits a synergistic effect
    with ionic liquid solvents and readily outperforms analogous
    oxidations in methylene chloride. Moreover, the ionic TEMPO
    could be recycled five times with no loss of activity.

  • Analysis of Pigments in the Printing Inks of the First Japanese Postage Stamps, the Hand-Engraved Issues

    Araki, Shuki; Kondo, Emi; Shibata, Tomohiro; Yokota,Takeshi; Marena, Suzuki, Hirashita, Tsunehisa Yamaguchi, Koichi; Matsumoto, Hirok; Murase, Yoshiaki

    Bulletin of the Chemical Society of Japan ( 日本化学会 )    2016.02  [Refereed]

    Research paper (scientific journal)   Multiple Authorship

  • Condensation of indoles and aldehydes in subcritical water without the addition of catalysts

    Tsunehisa Hirashita, Masaki Ogawa, Reina Hattori, Sota Okochi, Shuki Araki

    Bulletin of the Chemical Society of Japan   88   1760 - 1764   2015.09  [Refereed]

    Research paper (scientific journal)   Multiple Authorship

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Books

  • Indium compounds.(共著)

    Shuki Araki, Tsunehisa Hirashita (Part: Multiple Authorship )

    Thieme Chemistry  2011.03

  • Indium(III) Iodide.(共著)

    Tsunehisa Hirashita, Shuki Araki (Part: Multiple Authorship )

    John Wiley & Sons  2011.03

  • Indium and Gallium in “Comprehensive Organometallic Chemistry III”.(共著)

    Shuki Araki, Tsunehisa Hirashita (Part: Multiple Authorship )

    Elsevier  2006.12

  • Methyl lithium.(共著)

    Shuki Araki, Tsunehisa Hirashita (Part: Multiple Authorship )

    John Wiley & Sons  2006.04

  • In in Organic Synthesis in “Main Group Metals in Organic Synthesis” .(共著)

    Araki, S. and Hirashita, T. (Part: Multiple Authorship )

    Wiley-VCH  2004.05 ISBN: 9780080456476

  • Indium(I) Iodide (共著)

    Shuki Araki, Tsunehisa Hirashita (Part: Multiple Authorship )

    John Wiley & Sons  2002.10

  • Indium Trichloride.(共著)

    Araki, S. and Hirashita, T. (Part: Multiple Authorship )

    John Wiley & Sons  2002.10

  • Porous Titania Ceramics Prepared by Mimicking Silicified Woods in "Ceramic Processing Science VI".(共著)

    Hirashita, T.; Miyazaki, H.; Takase, H.; Kinoshita , N.; Ota, T. (Part: Multiple Authorship )

    American Ceramic Society  2001.09 ISBN: 978-1574981049

Review Papers

  • "jointly worked

      53   939 - 943   2008.12

    Introduction and explanation (commerce magazine)   Multiple Authorship

Presentations

  • メソイオン液体中におけるヘック反応

    倉林秀明・平下恒久・荒木修喜

    第49回 中部化学関係学協会支部連合秋季大会  2018.11  -  2018.11 

  • 1,3-ジ置換テトラゾリウム-5-オレート系メソイオン化合物のリチオ化を経由した官能基化

    前野正光,平下恒久,荒木修喜

    日本化学会第98春季年会  2018.03  -  2018.03 

  • Reactions Of Nitrosotetrazolium Salt

    松川裕太・平下恒久・荒木修喜

    RACI CENTENARY CONGRESS 2017  2017.07  -  2717.07 

  • Oxidation of Alcohols with a Novel Nitrosotetrazolium Organocatalys

    Yuta Matsukawa, Tsunehisa Hirashita, Shuki Araki

    IKCOC-13  2015.11  -  2015.11 

  • Photochemical Reaction of Organoindium Tetraphenylporphyrin Complexes

    ○Sachiko Nishihara, Kazuki Sugiyama, Tsunehisa Hirashita, Shuki Araki

    KCOC-12  2012.11  -  2012.11