HIRASHITA Tsunehisa

写真a

Affiliation Department etc.

Department of Life Science and Applied Chemistry
Department of Life Science and Applied Chemistry
Center for Research and Development in Higher Engineering-Education

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)

External Career

  • 2005.02
    -
    2006.02

    Delft University of Technology   Biocatalysis and Organic Chemistry Department of Biotechnology   Researcher  

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

  • Palladium-Catalyzed Selective o-Bromination of Mesoionic 1,3-Diphenyltetrazolium-5-olate: Switching the Directing Group from Nitrogen to Oxygen

    Harue Watanabe, Yuki Harada, Hideaki Kurabayashi, Yukinobu, Yamashita, Shiyogo Oizumi, Shuki Araki

    ChemistrySelect     2021  [Refereed]

    Research paper (scientific journal)   Multiple Authorship

    Pd-catalyzed bromination of mesoionic 1,3-diphenyltetrazolium-5-olate (1) was developed. In the presence of palladium acetate (5 mol%), N-bromosuccinimide (110 mol%), and p-toluenesulfonic acid (50 mol%) in 1,2-dichloroethane under reflux, olate 1 underwent bromination to give 1-(2-bromophenyl)-3-phenyltetrazolium-5-olate in a moderate yield as the major product, indicating that the 4-nitrogen atom acts as a directing group rather than the negatively charged oxygen atom. The X-ray-suitable crystals of the corresponding palladacycle were isolated from 1-mesityl-3-phentytetrazolium-5-olate and fully characterized. When both the o-positions of the 3-phenyl group were occupied by bromine atoms, o-bromination then occurred at the 1-phenyl group with the aid of the olate oxygen.

  • Preparative Synthesis of 1,3-Dialkyltetrazolium-5-thiolates from 1-Alkyltetrazole-5-thiols

    Hirashita, Tsunehisa; Murakami, Suguru ; Shoji, Takuo; Kurabayashi, Hideaki ; Araki, Shuki

    Bulletin of the Chemical Society of Japan     2021  [Refereed]

    Research paper (scientific journal)   Multiple Authorship

    Mesoionic 1,3-dialkyltetrazolium-5-thiolates can be prepared in good yields by alkylation of 1-alkyltetrazole-5-thiols with secondary alcohols in concentrated sulfuric acid. The thiolates are transformed into the corresponding olates through S-alkylation followed by hydrolysis. The olates were found to be liquid at room temperature and to work effectively as polar solvents. The use of a smaller amount of sulfuric acid led to drastically different products; S-bridged dimers linked by 1,2-dimethylethylene were formed as the major products.

  • The Mizoroki-Heck Reaction in Mesoionic 1-Butyl-3-methyltetrazolium-5-olate

    Hideaki Kurabayashi, Tsunehisa Hirashita, Shuki Araki

    Tetrahedron     2021  [Refereed]

    Research paper (scientific journal)   Multiple Authorship

    1-Butyl-3-methyltetrazolium-5-olate (1), a mesoionic compound, exists as a liquid at room temperature and can be used as a polar solvent for the Mizoroki-Heck reaction, wherein it has been proven to be a superior solvent to other solvents. The reaction of iodobenzene with ethyl acrylate in the presence of palladium acetate in mesoionic liquid 1 at 40 C for 24 h gave ethyl cinnamate in 78% yield in the absence of ligands, while the use of other solvents, such as [bmim][BF4], [bmim][PF6], and DMF gave lower yields (43%, 37%, and 17%, respectively) under the same conditions. Heck-type coupling reactions of electron-deficient or electron-rich aryl iodides and bromobenzenes with olefins (15 examples, 7%–97%) were performed in 1. When a phosphine ligand was added to the reaction mixture, aryl bromides could be used, and the mesoionic liquid containing the catalysts could be reused at least five times.

  • 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

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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

  • Palladium catalyzed cross-coupling reactions in mesoionic liquids

    KURABAYASHI Hideaki, HIRASHITA Tsunehisa

    日本化学会第100春季年会  2020.03  -  2020.03  日本化学会

  • イオン液体中における有機インジウム反応剤とカルボニル化合物の反応

    鈴木 進吾,平下 恒久

    第50回 中部化学関係学協会支部連合秋季大会  2019.11  -  2019.11 

  • Synthesis and Properties of Mesoionic Tetrazoliumthiolate-diiodine Adduct

    松川裕太,平下恒久

    日本化学会第99春季年会  2019.03  -  2019.03 

  • 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