Researcher Database

Tsuyoshi Mita
Creative Research Institution Institute for Chemical Reaction Design and Discovery
Specially Appointed Associate Professor

Researcher Profile and Settings

Affiliation

  • Creative Research Institution Institute for Chemical Reaction Design and Discovery

Job Title

  • Specially Appointed Associate Professor

Degree

  • Ph.D.(The University of Tokyo)

URL

Research funding number

  • 00548183

J-Global ID

Research Interests

  • パラジウム   コバルト   C-H結合活性化   イリド   アンモニウムイリド   カルベン   DFT計算   AFIR法   量子化学計算   固定化   二酸化炭素   アミノ酸   アミノスズ   イミン   フッ化セシウム   カルバニオン   セシウムフルオリド   アミノスルホン   不斉合成   アミノシラン   Stille型反応   遷移金属錯体   遷移金属錯体触媒   フェニルグリシン   

Research Areas

  • Nanotechnology/Materials / Energy chemistry
  • Nanotechnology/Materials / Green/sustainable/environmental chemistry
  • Life sciences / Bioorganic chemistry
  • Nanotechnology/Materials / Structural/physical organic chemistry
  • Nanotechnology/Materials / Synthetic organic chemistry
  • Life sciences / Pharmaceuticals - chemistry and drug development

Academic & Professional Experience

  • 2019/10 - Today JST, ERATO “Artificial Intelligence in Chemical Reaction Design and Discovery” (Project leader: Prof. Satoshi Maeda) A group leader in synthetic organic chemistry
  • 2019/04 - Today Hokkaido University Institute for Chemical Reaction Design and Discovery (WPI-ICReDD) Specially Appointed Associate Professor
  • 2009/04 - 2019/03 Hokkaido University Faculty of Pharmaceutical Sciences Assistant Professor
  • 2007/04 - 2009/03 Harvard University Department of Chemistry & Chemical Biology Postdoctoral Fellow
  • 2002/04 - 2004/03 Ajinomoto Co., INC. Process Research & Development, Pharmaceutical Research Laboratories Resercher

Education

  • 2004/04 - 2007/03  The University of Tokyo  Graduate School of Pharmaceutical Sciences
  • 2000/04 - 2002/03  Keio University  Graduate School of Science and Technology
  • 1996/04 - 2000/03  Keio University  Chemistry Department

Association Memberships

  • The AMERICAN CHEMICAL SOCIETY   THE SOCIETY OF SYNTHETIC ORGANIC CHEMISTRY, JAPAN   THE CHEMICAL SOCIETY OF JAPAN   THE PHARMACEUTICAL SOCIETY OF JAPAN   The Society of Pure & Applied Coordination Chemistry   

Research Activities

Published Papers

  • Ryosuke Shishido, Minami Uesugi, Rikuro Takahashi, Tsuyoshi Mita, Tatsuo Ishiyama, Koji Kubota, Hajime Ito
    Journal of the American Chemical Society 142 (33) 14125 - 14133 0002-7863 2020/07/22 [Refereed][Not invited]
  • Tsuyoshi Mita, Yu Harabuchi, Satoshi Maeda
    Chemical Science Royal Society of Chemistry 11 (29) 7569 - 7577 2020/05/22 [Refereed][Not invited]
  • Tsuyoshi Mita, Masashi Uchiyama, Yoshihiro Sato
    Advanced Synthesis & Catalysis 362 (6) 1275 - 1280 2020/03 [Refereed][Not invited]
  • Tsuyoshi Mita, Yoshihiro Sato
    Chemistry - An Asian Journal 14 (12) 2038 - 2047 2019/05 [Refereed][Invited]
  • Tsuyoshi Mita, Hiroki Masutani, Sho Ishii, Yoshihiro Sato
    Synlett 30 (7) 814 - 844 2019/03 [Refereed][Not invited]
  • Tsuyoshi Mita, Sho Ishii, Yuki Higuchi, Yoshihiro Sato
    Organic Letters 20 (23) 7603 - 7606 2018/11 [Refereed][Not invited]
  • Tsuyoshi Mita, Masashi Uchiyama, Kenichi Michigami, Yoshihiro Sato
    Beilstein Journal of Organic Chemistry 14 2012 - 2017 2018/08 [Refereed][Not invited]
  • Tsuyoshi Mita, Satoshi Hanagata, Kenichi Michigami, Yoshihiro Sato
    ORGANIC LETTERS 19 (21) 5876 - 5879 1523-7060 2017/11 [Refereed][Not invited]
     
    By using Co(acac)(2)/Xantphos with AlMe3, the C(sp(3))-H bonds of allylarene derivatives were cleaved for reaction with various ketones, affording the homoallylic alcohols in moderate to good yields. The branch/linear selectivity depended on the steric and electronic factors of the ketone electrophiles. The intermediate in this reaction is thought to be a low-valent allylcobalt(I) species, which exhibits high nucleophilicity toward ketones.
  • Yuki Higuchi, Tsuyoshi Mita, Yoshihiro Sato
    ORGANIC LETTERS 19 (10) 2710 - 2713 1523-7060 2017/05 [Refereed][Not invited]
     
    Arylative carboxylation of allenes proceeded in an intramolecular manner to afford the corresponding beta,gamma-unsaturated carboxylic adds in high yields using PdCl2/PAr3 (Ar = C6H4-p-CF3) and ZnEt2 under 1 atm of CO2. The intermediate of the cyclization/carboxylation sequence is thought to be a nucleophilic n(1)-allylethylpalladium, which reacts with CO2 at the gamma-position of palladium. The products obtained could be efficiently converted into 3-substituted indole-2-carboxylate derivatives. One-pot synthesis of strychnocarpine, a beta-carboline alkaloid, from the carboxylated product was also demonstrated.
  • Kenichi Michigami, Tsuyoshi Mita, Yoshihiro Sato
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 139 (17) 6094 - 6097 0002-7863 2017/05 [Refereed][Not invited]
     
    Catalytic carboxylation of the allylic C-(sp(3))-H bond of terminal alkenes with CO2 was developed with the aid of a Co/Xantphos complex. A wide range of allylarenes and 1,4-dienes were successfully transformed into the linear styrylacetic acid and hexa-3,5-dienoic acid derivatives in moderate to high yields, with excellent regioselectivity. The carboxylation showed remarkable functional group tolerability, so that selective addition to CO2 occurred in the presence of other carbonyl groups such as amide, ester, and ketone. Since styrylacetic acid derivatives can be readily converted into optically active gamma-butyrolactones through Sharpless asymmetric dihydroxylation, this allylic C(sp(3))-H carboxylation showcases a facile synthesis of gamma-butyrolactones from simple allylarenes via short steps.
  • Tsuyoshi Mita, Masumi Sugawara, Yoshihiro Sato
    JOURNAL OF ORGANIC CHEMISTRY 81 (12) 5236 - 5243 0022-3263 2016/06 [Refereed][Not invited]
     
    A simple, yet powerful protocol for alpha-amino acid synthesis using carbon dioxide (CO2) was developed. alpha-Amino silanes could undergo four successive reactions (formation of ammonium salt, carboxylation, esterification, and 2,3- or 1,2-Stevens rearrangement) in the presence of allylic or benzylic halides under a CO2 atmosphere (1 atm). It is noteworthy that carboxylation at the position adjacent to a nitrogen atom proceeded via an ammonium ylide intermediate under mild conditions.
  • Tsuyoshi Mita, Hiroyuki Tanaka, Yuki Higuchi, Yoshihiro Sato
    ORGANIC LETTERS 18 (11) 2754 - 2757 1523-7060 2016/06 [Refereed][Not invited]
     
    By using a palladium catalyst with ZnEt2, activated viriylcyclopropanes were successfully converted into the corresponding beta,gamma-unsaturated carboxylic acid's in high yields under a CO2 atmosphere (1 atm). The intermediate in this reaction is thought to be a nucleophilic eta-allylethylpalladium species, which would be produced from pi-allylpalladium and ZnEt2 (umpolung reactivity).
  • Tsuyoshi Mita, Keisuke Saito, Masumi Sugawara, Yoshihiro Sato
    CHEMISTRY-AN ASIAN JOURNAL 11 (10) 1528 - 1531 1861-4728 2016/05 [Refereed][Not invited]
     
    Enantioenriched N-tert-butylsulfonyl-alpha-amido si-lanes were successfully reacted with aldehydes, ketones, imines, and alpha,beta-unsaturated esters in the presence of a sub-stoichiometric amount of CsF (0.5 equiv) in 1,2-di-methoxyethane (DME) at -20 degrees C to afford the corresponding coupling products with up to 89% enantiospecificity in a retentive manner.
  • Tsuyoshi Mita, Kenta Suga, Kaori Sato, Yoshihiro Sato
    ORGANIC LETTERS 17 (21) 5276 - 5279 1523-7060 2015/11 [Refereed][Not invited]
     
    By using a strained four-membered ring disilane (3,4-benzo-1,1,2,2-tetraethyldisilacyclobutene) and CsF, a wide range of aryl, alkenyl, alkynyl, benzyl, allyl, and alkyl halides was successfully carboxylated under an ambient CO2 atmosphere (CO2 balloon) at room temperature within 2 h. In this carboxylation, a highly reactive silyl anion, which is generated from the disilane and CsF, is a key to facilitating the formation of a carbanion equivalent. The resulting anionic species can be trapped with CO2 to produce carboxylic acids with high efficiency.
  • Tsuyoshi Mita, Yuki Higuchi, Yoshihiro Sato
    CHEMISTRY-A EUROPEAN JOURNAL 21 (46) 16391 - 16394 0947-6539 2015/11 [Refereed][Not invited]
     
    Various allylic alcohols were carboxylated in the presence of a catalytic amount of PdCl2 and PPh3 using ZnEt2 as a stoichiometric transmetalation agent under a CO2 atmosphere (1atm). This carboxylation proceeded in a highly regioselective manner to afford branched carboxylic acids predominantly. The ,-unsaturated carboxylic acid thus obtained was successfully converted into an optically active -butyrolactone, a known intermediate of (R)-baclofen.
  • Mita Tsuyoshi
    有機合成化学協会誌 73 (8) 810 - 820 2015/08 [Refereed][Invited]
  • Tsuyoshi Mita, Hiroyuki Tanaka, Kenichi Michigami, Yoshihiro Sato
    SYNLETT 25 (9) 1291 - 1294 0936-5214 2014/06 [Refereed][Not invited]
     
    Carboxylation of 1-arylpyrazole derivatives was developed using a ruthenium-catalyzed ortho silylation in conjunction with fluoride-mediated carboxylation with carbon dioxide. The two nitrogen atoms of pyrazole play crucial roles in promoting ortho silylation via the formation of a five-membered ruthenacycle and in accelerating aryl anion formation by lowering the electron density of the aromatic ring.
  • Tsuyoshi Mita, Masumi Sugawara, Keisuke Saito, Yoshihiro Sato
    ORGANIC LETTERS 16 (11) 3028 - 3031 1523-7060 2014/06 [Refereed][Not invited]
     
    A catalytic enantioselective silylation of N-tertbutylsulfonylimines using a Cu secondary diamine complex was demonstrated. The resulting optically active alpha-amino silanes could be carboxylated under a CO2 atmosphere (1 atm) to afford the corresponding a-amino acids in a stereoretentive manner. This two-step sequence provides a new synthetic protocol for optically active a-amino acids from gaseous CO2 and imines in the presence of a catalytic amount of a chiral source.
  • Tsuyoshi Mita, Jianyang Chen, Yoshihiro Sato
    ORGANIC LETTERS 16 (8) 2200 - 2203 1523-7060 2014/04 [Refereed][Not invited]
     
    In the presence of three readily available chemicals, Mn powder, BF3 center dot OEt2, and LiCl, N-acyl-N,O-acetals were successfully converted into the corresponding alpha-amino acids (arylglycine derivatives) under 1 atm of a CO2 atmosphere in high yields. The LiCl additive is necessary in order to increase the solubility and the nucleophilicity of an organomanganese intermediate. The products thus obtained were transformed into free alpha-amino acids in two steps.
  • Tsuyoshi Mita, Yuki Higuchi, Yoshihiro Sato
    ORGANIC LETTERS 16 (1) 14 - 17 1523-7060 2014/01 [Refereed][Not invited]
     
    In the presence of CsF, a wide range of alpha-substituted alpha-siloxy silanes were carboxylated under a CO2 atmosphere (1 atm) via Brook rearrangement. A variety of alpha-substituents including aryl, alkenyl, and alkyl groups were tolerated to afford alpha-hydroxy acids in moderate-to-high yields. One-pot synthesis from aldehydes using PhMe2SiLi and CO2 was also possible, providing alpha-hydroxy acids without the isolation of an alpha-hydroxy silane.
  • Tsuyoshi Mita, Kenichi Michigami, Yoshihiro Sato
    CHEMISTRY-AN ASIAN JOURNAL 8 (12) 2970 - 2973 1861-4728 2013/12 [Refereed][Not invited]
  • Tsuyoshi Mita, Yuto Ikeda, Kenichi Michigami, Yoshihiro Sato
    Chemical Communications 49 (49) 5601 - 5603 1359-7345 2013/06/21 [Refereed][Not invited]
     
    An unprecedented catalytic C(sp3)-H triborylation at a single carbon was developed with the assistance of a nitrogen directing group. © 2013 The Royal Society of Chemistry.
  • Tsuyoshi Mita, Yuki Higuchi, Yoshihiro Sato
    Chemistry - A European Journal 19 (3) 1123 - 1128 0947-6539 2013/01/14 [Refereed][Not invited]
     
    α-Amino acids are essential resources for human life and are highly useful as building blocks for organic synthesis. The core framework of an α-amino acid can be divided into three basic components: an aldehyde, an amine, and carbon dioxide (CO2). We report herein that a one-step synthesis of α-amino acids has been successfully achieved from these three basic and inexpensive chemicals with a single operation, in which the mixture of an aldehyde, a sulfonamide, and gaseous CO2 was heated at 100 °C in the presence of Bu3Sn-SnBu3 and CsF. In this one-pot sequential protocol, two important intermediates (imine and α-amino stannane) are involved and the stannyl anion generated in situ plays a crucial role, particularly for the efficient stannylation of the imine in the presence of proton sources and for promoting retrostannylation of the undesired α-alkoxy stannane owing to its high stability and tolerance of the presence of proton sources. This methodology enabled the synthesis of a wide range of racemic arylglycine derivatives in high yields. Go retro! α-Amino acids are essential resources for human life and are highly useful as building blocks for organic synthesis. The core framework of an α-amino acid is retrosynthesized to an aldehyde, an amine, and carbon dioxide. A one-step synthesis of α-amin Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
  • Tsuyoshi Mita, Yoshihiro Sato
    Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry 71 (11) 1163 - 1171 0037-9980 2013 [Refereed][Invited]
     
    Carbon dioxide (CO2) is an abundant, inexpensive, relatively nontoxic, and renewable C1 source for organic synthesis, fixations of which have been intensively studied over the past decade. For the purpose of preparing valuable commodity chemicals from easily accessible starting materials through CO2 incorporation, we have made many efforts toward the development of α-amino acid synthesis from CO2 and imines. By changing the latent polarity of imino carbon by treatment of a stannyl or a silyl anion derived from CsF and bismetal reagents (Me3Si-SnBu3 or PhMe2Si-Bpin) with imine, we successfully developed a one-pot synthesis of N-Boc-α-amino acids from gaseous CO2 and N-Boc-α-amido sulfones (stable N-Boc-imine precursors). In addition, we have developed a one-pot α-amino acid synthesis from three basic components, CO2, an aldehyde, and a sulfonamide, promoted by Bu 3Sn-SnBu3 and CsF. Intermediates of these α-amino acid syntheses are imines and α-amino stannanes or α-amino silanes.
  • Tsuyoshi Mita, Jianyang Chen, Masumi Sugawara, Yoshihiro Sato
    ORGANIC LETTERS 14 (24) 6202 - 6205 1523-7060 2012/12 [Refereed][Not invited]
     
    In the presence of 1.1 equiv of PhMe2Si-Bpin, 5 equiv of CsF, and 20 mol % of TsOH center dot H2O, precursors of N-Boc-imines can be converted into the corresponding alpha-aryl or alpha-alkenyl glycine derivatives under gaseous CO2 in moderate-to-high yields with a single operation. alpha-Isobutenyl glycine thus obtained can be further derivatized into various types of alpha-amino acids including N-Boc-leucine, serine, and glycine derivatives in short steps.
  • Tsuyoshi Mita, Kenichi Michigami, Yoshihiro Sato
    ORGANIC LETTERS 14 (13) 3462 - 3465 1523-7060 2012/07 [Refereed][Not invited]
     
    One of the most challenging transformations in current organic chemistry is the catalytic carboxylation of a C(sp(3))-H bond using CO2 gas, an inexpensive and ubiquitous Cl source. A sequential protocol for C(sp(3))-H carboxylation by employing a nitrogen-directed, metal-assisted, C-H activation/catalytic silylation reaction in conjunction with fluoride-mediated carboxylation with CO2 was established. The carboxylation proceeded only at the benzylic C(sp(3))-Si bond, not at the aromatic C(sp(2))-Si, which is advantageous for further manipulations of the products.
  • Tsuyoshi Mita, Masumi Sugawara, Hiroyuki Hasegawa, Yoshihiro Sato
    JOURNAL OF ORGANIC CHEMISTRY 77 (5) 2159 - 2168 0022-3263 2012/03 [Refereed][Not invited]
     
    Incorporation reactions of carbon dioxide (CO2) with N-Boc-alpha\-amido and a-acetoxy stannanes were developed using CsF as a mild tin activator. Monoprotected alpha-amido stannanes could be used, and the corresponding arylglycine derivatives were obtained in moderate-to-high yields under 1 MPa (10 atm) of CO2 pressure. alpha-Acetoxy stannanes also underwent carboxylation to afford mandelic acid derivatives in excellent yields under ambient CO2 pressure. Both transformations enabled the synthesis of alpha-tertiary and alpha-quaternary carboxylic acid derivatives. In addition, the chirality of (S)-N-tert-butylsulfonyl-alpha-amido stannanes was transferred with up to 90% inversion of configuration at 100 degrees C.
  • Tsuyoshi Mita, Yuki Higuchi, Yoshihiro Sato
    SYNTHESIS-STUTTGART 44 (2) 194 - 200 0039-7881 2012/01 [Refereed][Not invited]
     
    Convenient and practical synthesis of N-Boc- and N-Cbz-alpha-amino stannanes from the corresponding a-amido sulfones was achieved. Yields of products are generally good to high because of the consequence of avoiding the isolation of unstable imine intermediates. The procedure is so simple that large-scale stannylation is possible without any difficulty.
  • Tsuyoshi Mita, Yuki Higuchi, Yoshihiro Sato
    ORGANIC LETTERS 13 (9) 2354 - 2357 1523-7060 2011/05 [Refereed][Not invited]
     
    In the presence of TMSSnBu3 and CsF, stannylation of N-Boc- and N-Cbz-alpha-amido sulfones proceeded very well to afford the corresponding alpha-amido stannanes in moderate-to-high yields. This reaction tolerated alpha-aryl-, alkenyl-, and alkyl-substituted alpha-amido sulfones as well as substrates containing either an ester or cyano moiety, which might be reactive with lithium or magnesium stannides employed in conventional stannylation.
  • Tsuyoshi Mita, Jianyang Chen, Masumi Sugawara, Yoshihiro Sato
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 50 (6) 1393 - 1396 1433-7851 2011 [Refereed][Not invited]
  • Tsuyoshi Mita, Eric N. Jacobsen
    SYNLETT 2009 (10) 1680 - 1684 0936-5214 2009/06 [Refereed][Not invited]
     
    Ring opening of aziridines with hydrogen chloride to form beta-chloroamine derivatives is catalyzed by a chiral phosphinothiourea derivative in high yields and with high enantioselectivities. On the basis of (31)P NMR studies, activation of HCl appears to proceed via quantitative protonation of the catalyst to afford a phosphonium chloride complex.
  • Ikuo Fujimori, Tsuyoshi Mita, Keisuke Maki, Motoo Shiro, Akihiro Sato, Sanae Furusho, Motomu Kanai, Masakatsu Shibasaki
    TETRAHEDRON 63 (26) 5820 - 5831 0040-4020 2007/06 [Refereed][Not invited]
     
    New chiral ligands (4 and 5) for polymetallic asymmetric catalysts were designed based on the hypothesis that the assembled structure should be stable when made from a stable module 8. A metal-ligand 5:6+mu-oxo+OH complex was generated from Gd((OPr)-Pr-i)(3) and 4 or 5, and this complex was an improved asymmetric catalyst for the desymmetrization of meso-aziridines with TMSCN and conjugate addition of TMSCN to alpha,beta-unsaturated N-acylpyrroles, compared to the previously reported catalysts derived from 1-3. These two groups of catalysts produced opposing enantioselectivity even though the ligands had the same chirality. The functional difference in the asymmetric catalysts is derived from differences in the higher-order structure of the polymetallic catalysts. (C) 2007 Elsevier Ltd. All rights reserved.
  • Tsuyoshi Mita, Nobuhisa Fukuda, Francesc X. Roca, Motomu Kanai, Masakatsu Shibasaki
    ORGANIC LETTERS 9 (2) 259 - 262 1523-7060 2007/01 [Refereed][Not invited]
     
    Catalytic asymmetric synthesis of Tamiflu, an important antiinfluenza drug, was achieved. After the catalytic enantioselective desymmetrization of meso-aziridine 3 with TMSN3, using a Y catalyst (1 mol %) derived from ligand 2, an allylic oxygen function and C1 unit on the CC double bond were introduced through cyanophosphorylation of enone and allylic substitution with an oxygen nucleophile. This second generation route of Tamiflu is more practical than our previously reported route.
  • Ikuo Fujimori, Tsuyoshi Mita, Keisuke Maki, Motoo Shiro, Akihiro Sato, Sanae Furusho, Motomu Kanai, Masakatsu Shibasaki
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 128 (51) 16438 - 16439 0002-7863 2006/12 [Refereed][Not invited]
  • Yuhei Fukuta, Tsuyoshi Mita, Nobuhisa Fukuda, Motomu Kanai, Masakatsu Shibasaki
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 128 (19) 6312 - 6313 0002-7863 2006/05 [Refereed][Not invited]
  • Nobuki Kato, Tsuyoshi Mita, Motomu Kanai, Bruno Therrien, Masaki Kawano, Kentaro Yamaguchi, Hiroshi Danjo, Yoshihisa Sei, Akihiro Sato, Sanae Furusho, Masakatsu Shibasaki
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 128 (21) 6768 - 6769 0002-7863 2006/05 [Refereed][Not invited]
  • T Mita, L Fujimori, R Wada, J Wen, ML Kanai, M Shibasaki
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 127 (32) 11252 - 11253 0002-7863 2005/08 [Refereed][Not invited]
  • S Kezuka, T Mita, Iwakura, I, T Ikeno, T Yamada
    JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN 63 (6) 604 - 615 0037-9980 2005/06 [Refereed][Not invited]
     
    This article is focused on the chiral Lewis acid catalyses by, the optically active ketoiminato-cobalt complexes. Screening of the central metal of the ketoiminato complex catalysts for the enantioselective hetero Diels-Alder reaction revealed that cobalt was the most effective for affording the corresponding pyranone derivatives. The corresponding cationic cobalt(III) complexes were developed as an efficient Lewis acid catalyst and subjected to the hetero Diels-Alder reaction and the carbonyl-ene reaction. It was found that their counter anions significantly influenced the reactivity and the enantio selectivity in the carbonyl-ene reaction. The cationic cobalt(III) complexes could be employed as the efficient catalysts for the enantioselective 1,3-dipolar cycloaddition reaction. Because of the competitive coordination. of the nitrone, the 1,3-dipolar cycloaddition with the monodentate alpha,beta-unsaturated aldehyde has been limited to several catalyses, although these cationic cobalt(III) complexes effectively catalyzed the reaction to afford the isoxazoline derivative with high-to-excellent stereoselectivities. These types of cobalt complex catalysts could be applied to the enantioselective Henry reaction even in the presence of amine bases, and the enantioselective chemical fixation of carbon dioxide to obtain the optically active cyclic carbonate.
  • T Mita, K Sasaki, M Kanai, M Shibasaki
    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 127 (2) 514 - 515 0002-7863 2005/01 [Refereed][Not invited]
  • S Kezuka, N Ohtsuki, T Mita, Y Kogami, T Ashizawa, T Ikeno, T Yamada
    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN 76 (11) 2197 - 2207 0009-2673 2003/11 [Refereed][Not invited]
     
    The enantioselective 1,3-dipolar cycloaddition reaction of nitrones with alpha,beta-unsaturated aldehydes was realized using 3-oxobutylideneaminatocobalt complex catalysts. Varieties of the cobalt(II) and cobalt(III) complexes were screened and the cationic cobalt(III) complex with hexafluoroantimonate was found to be the most effective for the catalytic enantioselective 1,3-dipolar cycloaddition reaction. In the presence of the cobalt(III) hexafluoroantimonate complex, the enantioselective 1,3-dipolar cycloaddition reaction of various nitrones with alpha,beta-unsaturated aldehydes afforded the corresponding isoxazolidines in high yields and with high enantioselectivities. The absolute configuration of the optically active products was determined by X-ray analysis. Reasonable explanations for the enantioselection in the present 1,3-dipolar cycloaddition reaction catalyzed by the 3-oxobutylideneaminatocobalt complex were proposed.
  • Enantioselective 1,3-dipolar cycloaddition reactions between nitrones and alpha-substituted alpha,beta-unsaturated aldehydes catalyzed by chiral cationic cobalt(III) complexes
    N Ohtsuki, S Kezuka, Y Kogami, T Mita, T Ashizawa, T Ikeno, T Yamada
    SYNTHESIS-STUTTGART (9) 1462 - 1466 0039-7881 2003/07 [Refereed][Not invited]
     
    The optically active beta-ketoiminato cationic cobalt(III) complexes catalyzed the 1,3-dipolar cycloaddition reaction of nitrones with alpha,beta-unsaturated aldehydes. In the reaction of nitrones derived from 2-halobenzaldehyde, excellent endo-selectivities and high enantioselectivities were observed. The alpha-substituted alpha,beta-unsaturated aldehyde, such as 2-benzylpropenal, afforded the corresponding isoxazolidine in high stereoselectivity.
  • T Mita, N Ohtsuki, T Ikeno, T Yamada
    ORGANIC LETTERS 4 (15) 2457 - 2460 1523-7060 2002/07 [Refereed][Not invited]
     
    [GRAPHIC] The optically active beta-ketoiminato cationic cobalt(Ill) complexes were employed as efficient Lewis acid catalysts for the enantioselective 1,3-dipolar cycloaddition reaction of alpha,beta-unsaturated aldehydes with nitrones. Excellent endo selectivities and high enantioselectivities were achieved in the cycloaddition reaction of 1-cyclopentene-1-carbaldehyde and the nitrones derived from 2-halobenzaidehyde.
  • S. Kezuka, T. Mita, N. Ohtsuki, T. Ikeno, T. Yamada
    Bulletin of the Chemical Society of Japan 74 (7) 1333 - 1342 0009-2673 2001/07 [Refereed][Not invited]
     
    Optically active 3-oxobutylideneaminatocobalt(III) complexes were developed as effective catalysts for the enantioselective hetero Diels-Alder reaction of aromatic and aliphatic aldehydes with 3-(t-butyldimethylsilyloxy)-1-methoxy-1,3-butadiene. In the presence of the highly active cationic cobalt(III) complex, the hetero Diels-Alder reactions proceeded to afford the corresponding dihydropyran-4-ones with high performance and high enantioselectivities. The reaction with aromatic aldehydes substituted by a coordinating group at the ortho position proceeded more smoothly.
  • S Kezuka, T Mita, N Ohtsuki, T Ikeno, T Yamada
    CHEMISTRY LETTERS (7) 824 - 825 0366-7022 2000/07 [Refereed][Not invited]
     
    Optically active beta-ketoiminato cobalt(III) complexes were developed for use as effective catalysts of the enantioselective hetero Diels-Alder reaction of aryl and alkyl aldehydes with 1-methoxy-[3-(tert-butyldimethylsilyl)oxy]1,3-butadiene. In the presence of 5 mol% cationic cobalt(III) triflate complexes derived from optically active 1,2-bis(3,5-dimethylphenyl)-1,2-ethylenediamine, the hetero Diels-Alder reaction of p-nitrobenzaldehyde proceeded in 94% yield with 94% ee.
  • T Yamada, S Kezuka, T Mita, T Ikeno
    HETEROCYCLES 52 (3) 1041 - + 0385-5414 2000/03 [Refereed][Not invited]
     
    Among various aldiminato metal complexes, the optically active cobalt(II) complex efficiently catalyzed the enantioselective hetero Diels-Alder reaction of aromatic aldehydes with 1-methoxy-[3-(tert-butyldimethylsilyl)oxy]-1,3-butadiene. In the presence of 0.5 mol% of the catalyst, the reaction smoothly proceeded and ortho substituents of the dienophiles that could chelate to the catalyst significantly accelerated the reaction to improve the chemical and optical yields.

Books etc

  • 二酸化炭素を用いた化学品製造技術
    杉本 裕, 室井 髙城, 矢部 智宏, 小河 脩平, 関根 泰, 梅田 実, 内田 希, 白仁田 沙代子, 井出 裕介, 武石 薫, 中田 一弥, 寺島 千晶, 勝又 健一, 藤嶋 昭, 栄長 泰明, 川島 慎悟, 三上 幸一, 山田 徹, 関根 康平, 藤原 哲晶, 辻 康之, 木村 正成, 美多 剛, 佐藤 美洋, 高野 一史, 崔 準哲, 安田 弘之, 岡田 昌樹, 冨重 圭一, 榧木 啓人, 深谷 訓久, 古賀 舞都, 富永 洋一, 三宅 信寿, 青柳 直人, 落合 文吾, 遠藤 剛, 松井 南, 米山 賢, 中野 遼, 野崎 京子 (Joint work)
    S&T出版 2016/04 (ISBN: 4907002548) 306
  • Masakatsu Shibasaki, Motomu Kanai, Tsuyoshi Mita, Scott E. Denmark (Joint workChapter 1 The Catalytic Asymmetric Strecker Reaction)
    Wiley-Interscience 2008/03 (ISBN: 047025453X) 656 1-119
  • Tsuyoshi Mita, 東京図書編集部 (合格体験記 大学院でもう一度研究を!)
    東京図書 2006/01 (ISBN: 4489007140) 251 170-171

Conference Activities & Talks

MISC

Industrial Property Rights

Awards & Honors

  • 2020 宇部興産学術振興財団 第60回学術奨励賞
     計算科学主導による革新的有機合成反応の開発 
    受賞者: Tsuyoshi Mita
  • 2018 Institut Kimia Malaysia (Malaysian Institute of Chemistry) Lecture Award of ICPAC Langkawi 2018
     
    受賞者: Tsuyoshi Mita
  • 2016 公益財団法人 Chemist Award BCA in MSD Life Science Foundation, Japan
     二酸化炭素を用いた炭素-炭素結合生成を伴うカルボン酸誘導体の新規合成法の開発 
    受賞者: Tsuyoshi Mita
  • 2014 北海道大学 Hokkaido University President’s Award for Research Excellence, Japan
     
    受賞者: Tsuyoshi Mita
  • 2014 The Society of Synthetic Organic Chemistry, Japan Incentive Award in Synthetic Organic Chemistry, Japan
     二酸化炭素を一炭素源として用いた新規カルボキシル化反応の開発 
    受賞者: Tsuyoshi Mita
  • 2009 有機合成化学協会 Tosoh Corporation Award in Synthetic Organic Chemistry, Japan
     二酸化炭素ガスを用いるアミノ酸の化学合成 
    受賞者: Tsuyoshi Mita

Research Grants & Projects

  • 文部科学省:科学研究費補助金(基盤研究(C))
    Date (from‐to) : 2018/04 -2021/03 
    Author : Tsuyoshi Mita
  • 秋山記念生命科学振興財団:2020 年度 研究助成 <一般>
    Date (from‐to) : 2020 
    Author : Tsuyoshi Mita
  • Ube Industries Foundation:第60回学術奨励賞
    Date (from‐to) : 2020 
    Author : Tsuyoshi Mita
  • Astellas Foundation for Research on Metabolic Disorders:Research Fellowship
    Date (from‐to) : 2019 
    Author : Tsuyoshi Mita
  • 武田科学振興財団:薬学系研究助成
    Date (from‐to) : 2018 
    Author : Tsuyoshi Mita
  • 住友財団:基礎科学研究助成
    Date (from‐to) : 2018 
    Author : Tsuyoshi Mita
  • 文部科学省:科学研究費補助金(基盤研究(C))
    Date (from‐to) : 2014/04 -2017/03 
    Author : Tsuyoshi Mita
  • 内藤記念科学振興財団:内藤記念科学奨励金・研究助成
    Date (from‐to) : 2017 
    Author : Tsuyoshi Mita
  • 北海道科学技術総合振興センター(略称:ノーステック財団):若手研究人材・ネットワーク育成補助金(Talent補助金)
    Date (from‐to) : 2016 
    Author : Tsuyoshi Mita
  • 文部科学省:科学研究費補助金(若手研究(B))
    Date (from‐to) : 2012/04 -2014/03 
    Author : Tsuyoshi Mita
     
    平成24年度は、二酸化炭素ガスを用いる光学活性なα-アミノ酸の合成を目指して、その最初のステップであるイミンに対する触媒的不斉シリル化の検討を精力的に行った。まず、調製が容易なシリルボロン試薬 (PhMe2Si-Bpin) を用いてキラル銅触媒によるN-スルホニルイミンへの触媒的不斉反応を開発するべく、種々の銅塩、および光学活性配位子の検討を網羅的に行った。その結果、一価のCuOTf1/2C6H6錯体を用い、リン系の不斉配位子を用いた場合に最高35% eeの不斉収率で目的のシリル化体が得られることがわかった。リン系の配位子を用いてこれ以上不斉収率を向上させることが困難であったため、次にアミン系の不斉配位子の検討を行ったところ、キラルな1,2-ジアミンを用いた場合に最高83% eeで目的のα-アミノシラン化合物が得られた。このものからは、一回の再結晶操作で光学的に純粋な単結晶を得ることができたため、X線結晶構造解析により正確な立体構造を決定し、得られたフラックのパラメータよりα-アミノシランの絶対立体配置をRと決定した。このN-スルホニルアミノシランは、フッ化セシウム存在下、一気圧の二酸化炭素ガスをDMF中-30℃で作用させることで、キラリティー若干の低下が観測されたものの、S体のα-アミノ酸誘導体(絶対立体配置の表記が反転)へ立体保持で変換できることがわかった。これより、二酸化炭素を一炭素源としたα-アミノ酸の不斉合成法の開発を達成することができた。
  • Ministry of Education, Culture, Sports, Science and Technology:Grants-in-Aid for Scientific Research(若手研究(B))
    Date (from‐to) : 2010/04 -2012/03 
    Author : Tsuyoshi Mita
     
    Carbon dioxide is an abundant, inexpensive, and nontoxic C1 unit ; however, its inertness and gaseous character sometimes hamper its use for efficient C-C bond-forming reactions in organic synthesis. Despite its difficulty, we have successfully developed one-potα-amino acid synthesis from imines using carbon dioxide though C-C bond-formation.
  • 文部科学省:科学研究費補助金(若手研究(スタートアップ), 研究活動スタート支援)
    Date (from‐to) : 2009/10 -2010/03 
    Author : Tsuyoshi Mita
     
    まず研究計画に従い、窒素原子上に様々な保護基を有するイミンを調製し、CO_2およびNi(COD)_2を用いたアザニッケラサイクル形成の検討を行った。しかし、いかなる条件においても目的とするアザニッケラサイクルの生成は確認できなかった。また、塩酸により加水分解したところ、目的とするアミノ酸誘導体の代わりに、イミンが還元されたアミン、もしくはイミン炭素とCO_2の酸素原子が反応して生成したと考えられるアミド誘導体が合わせて30%程度得られ、残りは原料回収であった。また、当初の計画通り、キレート効果を期待してイミンの窒素原子上に配位性の置換基を有した基質も試みたが、優位な差は観測されず、望みのアミノ酸誘導体は得ることはできなかった。そこで、大胆に合成戦略を変更し、α-アミノスズ誘導体を別途調製し、パラジウム、およびニッケル等の遷移金属錯体触媒を用いたCO_2とのStille型反応への展開を考えた。いくつかの既存の配位子を用いて反応を試みたところ、セシウムフルオリド(CsF)をスズの活性化剤として用いた際にCO_2と反応してアミノ酸誘導体が得られることがわかった。その後のコントロール実験より、遷移金属錯体触媒は本反応には必須ではなく、CsFのフッ素アニオンがスズを攻撃し、生じたカルボアニオンがCO_2へ求核付加していることが明らかとなった。いずれにせよCO_2をカルボン酸ユニットとして用い目的とするアミノ酸が得られたことから、今後はイミンへのシリルスズの付加(ビスメタル化)、続くCsFによるCO_2の導入反応をワンポットで行うとで、一般性の高いアミノ酸合成法の構築を成し遂げたい。
  • 上原記念生命科学財団:研究奨励金
    Date (from‐to) : 2010 
    Author : Tsuyoshi Mita
  • 二酸化炭素ガスを用いるアミノ酸の化学合成
    東ソー:研究企画賞助成金
    Date (from‐to) : 2009 
    Author : Tsuyoshi Mita

Educational Activities

Teaching Experience

  • Hokkaido Summer Institute 2018【Advanced Organometallic Chemistry for Synthetic Organic Chemistry】Hokkaido Summer Institute 2018【Advanced Organometallic Chemistry for Synthetic Organic Chemistry】 Hokkaido University

Committee Membership

  • 2018/02 -2020/02   The Society of Synthetic Organic Chemistry, Japan   Regional Editor
  • 2017 -2017   第29回万有札幌シンポジウム   事務局
  • 2016 -2016   第33回有機合成化学セミナー   運営委員
  • 2012 -2012   第24回万有札幌シンポジウム   事務局


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