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Development of acid-base hybrid organocatalysts and their application to unprecedented organic synthesis

Research Project

Project/Area Number 18H01975
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionTokyo University of Agriculture and Technology (2020-2022)
Kyoto University (2018-2019)

Principal Investigator

Kano Taichi  東京農工大学, 工学(系)研究科(研究院), 教授 (40372560)

Project Period (FY) 2018-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥17,160,000 (Direct Cost: ¥13,200,000、Indirect Cost: ¥3,960,000)
Fiscal Year 2021: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2020: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2019: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2018: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Keywords有機触媒 / 有機酸触媒 / 有機塩基触媒 / アミン触媒 / 不斉合成 / 有機分子触媒 / 酸塩基複合触媒 / マンニッヒ反応 / アミノ酸 / 酸触媒 / 塩基触媒 / アミン有機触媒 / 不斉触媒反応 / 環化反応
Outline of Final Research Achievements

In this study, we have developed acid-base hybrid organocatalysts that have both acidic and basic functional groups. A number of organocatalysts with both acidic and basic functional groups including amino acids have been reported. However, when acidic and basic functional groups coexist, they form acid-base complexes to inactivate the catalyst. We have developed novel catalysts by introducing both acidic and basic functional groups into a rigid framework to suppress the formation of intramolecular acid-base complexes. These acid-base hybrid organocatalysts showed sufficient reactivity and were found to be effective for novel asymmetric reactions.

Academic Significance and Societal Importance of the Research Achievements

本研究では、高い活性や選択性を示す酸塩基複合触媒を設計するためには、その酸性官能基と塩基性官能基の双方が接触しないよう、剛直な基本構造上に配置することが重要であることが明らかとなった。従来は触媒の土台となる剛直な基本構造としてビナフチル化合物が汎用されていたが、原料の調達やその修飾は容易ではなかった。本研究ではそれに代わる新しい基本構造を見出し、その簡便な合成法も確立した。本研究は、今後の触媒設計の際の新たな指針となり得る。

Report

(5 results)
  • 2022 Final Research Report ( PDF )
  • 2021 Annual Research Report
  • 2020 Annual Research Report
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • Research Products

    (49 results)

All 2022 2021 2020 2019 2018 Other

All Int'l Joint Research (2 results) Journal Article (27 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 27 results,  Open Access: 1 results) Presentation (20 results)

  • [Int'l Joint Research] Ruhr University Bochum(ドイツ)

    • Related Report
      2021 Annual Research Report
  • [Int'l Joint Research] Lanzhou Institute of Chemical Physics(中国)

    • Related Report
      2020 Annual Research Report
  • [Journal Article] Design and Synthesis of Phenylcyclopropane-based Chiral Amine Catalysts and Their Application in Asymmetric Reactions2022

    • Author(s)
      本間千裕、加納太一
    • Journal Title

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 80 Issue: 2 Pages: 92-102

    • DOI

      10.5059/yukigoseikyokaishi.80.92

    • NAID

      130008158523

    • ISSN
      0037-9980, 1883-6526
    • Year and Date
      2022-02-01
    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Design and Synthesis of Phenylcyclopropane-based Chiral Amine Catalysts and Their Application in Asymmetric Reactions2022

    • Author(s)
      本間千裕、加納太一
    • Journal Title

      有機合成化学協会誌

      Volume: 80 Pages: 92-102

    • NAID

      130008158523

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Practical Asymmetric Synthesis of Chiral Sulfoximines via Sulfur-Selective Alkylation2022

    • Author(s)
      Y. Maeda, S. Hamada, Y. Aota, K. Otsubo, T. Kano, K. Maruoka
    • Journal Title

      J. Org. Chem.

      Volume: 87 Issue: 5 Pages: 3652-3660

    • DOI

      10.1021/acs.joc.1c02424

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] The Design and Synthesis of Phenylcyclopropane-Based Secondary Amine Catalysts and Their Applications in Asymmetric Reactions2022

    • Author(s)
      Kano Taichi、Takeshima Aika
    • Journal Title

      Synlett

      Volume: - Issue: 18 Pages: 1778-1787

    • DOI

      10.1055/a-1796-7387

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] VCD spectroscopy distinguishes the enamine and iminium ion of a 1,1′-binaphthyl azepine2022

    • Author(s)
      Golub Tino P.、Kano Taichi、Maruoka Keiji、Merten Christian
    • Journal Title

      Chemical Communications

      Volume: 58 Issue: 60 Pages: 8412-8415

    • DOI

      10.1039/d2cc02863h

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Construction of Chiral α-tert-Amine Scaffolds via Amine-catalyzed Asymmetric Mannich Reactions of Alkyl-substituted Ketimines2021

    • Author(s)
      Chihiro Homma, Aika Takeshima, Taichi Kano, Keiji Maruoka
    • Journal Title

      Chemical Science

      Volume: 12 Issue: 4 Pages: 1445-1450

    • DOI

      10.1039/d0sc05269h

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Asymmetric α-Hydroxylation of α-Aryl-δ-lactams with Molecular Oxygenunder Phase-Transfer Conditions2021

    • Author(s)
      Tomoaki Inukai, Taichi Kano, Keiji Maruoka
    • Journal Title

      Organic Letters

      Volume: 23 Issue: 3 Pages: 792-796

    • DOI

      10.1021/acs.orglett.0c04022

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Bifunctional Amino Sulfonamide-catalyzed Asymmetric Conjugate Addition to Alkenyl Alkynyl Ketimines as Enone Surrogates2021

    • Author(s)
      Chihiro Homma, Taichi Kano, Keiji Maruoka
    • Journal Title

      Chemical Communications

      Volume: 57 Issue: 22 Pages: 2808-2811

    • DOI

      10.1039/d0cc07842e

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Alkynyl Z-Ketimines and Their Application in Amine-catalyzed Asymmetric Mannich Reactions and Conjugate Addition2021

    • Author(s)
      Chihiro Homma, Masahiro Yamanaka, Taichi Kano, Keiji Maruoka
    • Journal Title

      Tetrahedron

      Volume: 91 Pages: 132225-132225

    • DOI

      10.1016/j.tet.2021.132225

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ni-Catalyzed C(sp2)-H Alkylation of N-Quinolylbenzamide Using Alkylsilyl Peroxides as Structurally Diverse Alkyl Sources2021

    • Author(s)
      Saori Tsuzuki, Shunya Sakurai, Akira Matsumoto, Taichi Kano, Keiji Maruoka
    • Journal Title

      Chemical Communications

      Volume: 57 Issue: 64 Pages: 7942-7945

    • DOI

      10.1039/d1cc02983e

    • Related Report
      2021 Annual Research Report 2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cu-Catalyzed O-alkylation of phenol derivatives with alkylsilyl peroxides2021

    • Author(s)
      Sakurai Shunya、Kano Taichi、Maruoka Keiji
    • Journal Title

      Chemical Communications

      Volume: 57 Issue: 1 Pages: 81-84

    • DOI

      10.1039/d0cc07305a

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Construction of a Quaternary Carbon Center by Catalytic Asymmetric Alkylation of 3-Arylpiperidin-2-ones under Phase-Transfer Conditions2020

    • Author(s)
      T. Inukai, T. Kano, and K. Maruoka
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 59 Issue: 6 Pages: 2211-2214

    • DOI

      10.1002/anie.201913518

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Bronsted Acid-Catalyzed Intramolecular α-Arylation of Ketones with Phenolic Nucleophiles via Oxy-Allyl Cation Intermediates2020

    • Author(s)
      Aota Yusuke、Doko Yuki、Kano Taichi、Maruoka Keiji
    • Journal Title

      European Journal of Organic Chemistry

      Volume: 2020 Issue: 12 Pages: 1907-1911

    • DOI

      10.1002/ejoc.202000169

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Synthesis of Monosaccharide Analogues by Two-Step Sequential Enamine Catalysis: Benzoyloxylation and Aldol Reaction2020

    • Author(s)
      Shimogaki Mio、Takeshima Aika、Kano Taichi、Maruoka Keiji
    • Journal Title

      European Journal of Organic Chemistry

      Volume: - Issue: 14 Pages: 2028-2032

    • DOI

      10.1002/ejoc.202000073

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Development of Ketone-Based Brominating Agents (KBA) for the Practical Asymmetric α-Bromination of Aldehydes Catalyzed by Tritylpyrrolidine2020

    • Author(s)
      Takeshima Aika、Shimogaki Mio、Kano Taichi、Maruoka Keiji
    • Journal Title

      ACS Catalysis

      Volume: - Issue: 11 Pages: 5959-5963

    • DOI

      10.1021/acscatal.0c01596

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Organocatalytic Formal (3 + 2) Cycloaddition toward Chiral Pyrrolo[1,2-a]indoles via Dynamic Kinetic Resolution of Allene Intermediates2020

    • Author(s)
      Jian-Fei Bai, Lulu Zhao, Fang Wang, Fachao Yan, Taichi Kano, Keiji Maruoka, Yuehui Li
    • Journal Title

      Organic Letters

      Volume: 22 Issue: 14 Pages: 5439-5445

    • DOI

      10.1021/acs.orglett.0c01812

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Synthesis of Electron-Deficient Chiral Biphenols and Their Applications in Catalytic Asymmetric Reactions2020

    • Author(s)
      Kento Yasumoto, Taichi Kano, Keiji Maruoka
    • Journal Title

      Journal of Organic Chemistry

      Volume: 85 Issue: 15 Pages: 10232-10239

    • DOI

      10.1021/acs.joc.0c01116

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Cu-Catalyzed Enantioselective Alkylarylation of Vinylarenes Enabled by Chiral Binaphthyl?BOX Hybrid Ligands2020

    • Author(s)
      Sakurai Shunya、Matsumoto Akira、Kano Taichi、Maruoka Keiji
    • Journal Title

      Journal of the American Chemical Society

      Volume: 142 Issue: 45 Pages: 19017-19022

    • DOI

      10.1021/jacs.0c09008

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] CuCl2‐Mediated Oxidative Intramolecular α‐Arylation of Ketones with Phenolic Nucleophiles via Oxy‐Allyl Cation Intermediates2020

    • Author(s)
      T. Mochimatsu, Y. Aota, T. Kano, and K. Maruoka
    • Journal Title

      Chem. Asian J.

      Volume: 15 Issue: 22 Pages: 3816-3819

    • DOI

      10.1002/asia.202001032

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Synthesis of Chiral Sulfoximines via the S-Arylation of Sulfinamides2019

    • Author(s)
      Y. Aota, T. Kano, and K. Maruoka
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 141 Issue: 49 Pages: 19263-19268

    • DOI

      10.1021/jacs.9b11298

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Efficient Synthesis of Cyclic Sulfoximines from N-Propargylsulfinamides through Sulfur-Carbon Bond Formation2019

    • Author(s)
      Y. Aota, Y. Maeda, T. Kano, and K. Maruoka
    • Journal Title

      Chem.- Eur. J.

      Volume: 25 Issue: 69 Pages: 15755-15758

    • DOI

      10.1002/chem.201904501

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Synthesis of Chiral Sulfoximines through the S-Alkylation of Sulfinamides2019

    • Author(s)
      Y. Aota, T. Kano, and K. Maruoka
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 58 Issue: 49 Pages: 17661-17665

    • DOI

      10.1002/anie.201911021

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of Phenylcyclopropane-Based Secondary Amine Catalysts and Their Applications in Enamine Catalysis2019

    • Author(s)
      A. Takeshima, T. Kano, and K. Maruoka
    • Journal Title

      Org. Lett.

      Volume: 21 Issue: 19 Pages: 8071-8074

    • DOI

      10.1021/acs.orglett.9b03070

    • NAID

      120006731151

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Synthesis of Chiral 1,4-Enynes through Organocatalytic Alkenylation of Propargyl Alcohols with Trialkenylboroxines2019

    • Author(s)
      J.-F. Bai, K. Yasumoto, T. Kano, and K. Maruoka
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 58 Issue: 26 Pages: 8898-8901

    • DOI

      10.1002/anie.201904520

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] One-Pot Synthesis of Less Accessible N-Boc-Propargylic Amines Through BF3-Catalyzed Alkynylation and Allylation Using Boronic Esters2019

    • Author(s)
      K. Yasumoto, T. Kano, and K. Maruoka
    • Journal Title

      Org. Lett.

      Volume: 21 Issue: 9 Pages: 3214-3217

    • DOI

      10.1021/acs.orglett.9b00931

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of 1-Aminoindenes through Aza-Prins-Type Cyclization2018

    • Author(s)
      J.-F. Bai, K. Yasumoto, T. Kano, and K. Maruoka
    • Journal Title

      Chemistry;Eur. J.

      Volume: 24 Issue: 41 Pages: 10320-10323

    • DOI

      10.1002/chem.201802448

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] BF3-Catalyzed Synthesis of Cyclic Carbamates from Boc-Protected Aminals and Alkynes2018

    • Author(s)
      T. Kano, K. Yasumoto, and K. Maruoka
    • Journal Title

      Asian J. Org. Chem.

      Volume: 7 Issue: 8 Pages: 1575-157

    • DOI

      10.1002/ajoc.201800289

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Presentation] Asymmetric Synthesis of Chiral Sulfimides Through the O-Alkylation of Chiral Sulfinamides and Addition of Carbon Nucleophiles2022

    • Author(s)
      都築咲保里、加納太一
    • Organizer
      第8回野依フォーラム若手育成塾
    • Related Report
      2021 Annual Research Report
  • [Presentation] アミノ酸触媒を用いた不斉アルドール反応による動的速度論的分割を経た三連続不斉点の構築2022

    • Author(s)
      日川涼雅、下垣実央、加納太一
    • Organizer
      第38回有機合成化学セミナー
    • Related Report
      2021 Annual Research Report
  • [Presentation] 一級アミン触媒を用いた不斉アルドール反応による動的速度論的分割を経た三連続不斉点の構築2022

    • Author(s)
      日川涼雅、下垣実央、加納太一
    • Organizer
      第12回CSJ化学フェスタ
    • Related Report
      2021 Annual Research Report
  • [Presentation] 臭素数の異なるブロモカルボニル化合物間のクロスカップリング反応の開発2022

    • Author(s)
      武島愛夏、加納太一
    • Organizer
      2022ハロゲン利用ミニシンポジウム
    • Related Report
      2021 Annual Research Report
  • [Presentation] 臭素数の異なるブロモカルボニル化合物間のクロスカップリング反応の開発2022

    • Author(s)
      武島愛夏、加納太一
    • Organizer
      第15回 有機触媒シンポジウム
    • Related Report
      2021 Annual Research Report
  • [Presentation] 有機亜鉛試薬を用いた2種類のブロモカルボニル化合物を原料とする多置換フランのワンポット合成2022

    • Author(s)
      引間諒、武島愛夏、加納太一
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Et2Zn-Mediated Cross-Coupling Reactions between Dibromoketones and Monobromo Carbonyl Compounds2022

    • Author(s)
      武島愛夏、加納太一
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Asymmetric Synthesis of Chiral Sulfimides through the O-Alkylation of Chiral Sulfinamides2022

    • Author(s)
      都築咲保里、加納太一
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] スルフィンアミドの硫黄選択的アリール化反応による光学活性なスルホキシイミンの実用的合成法の開発2022

    • Author(s)
      東咲良、加納太一
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] アミノ酸触媒を用いた不斉アルドール反応による動的速度論的分割を経た三連続不斉点の構築2022

    • Author(s)
      日川涼雅、下垣実央、加納太一
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] ハイブリッド銅触媒系によるトリアルケニルボロキシンのエノンジエステルへの不斉共役付加反応の開発2022

    • Author(s)
      國友紀孝、安本健人、加納太一
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] アミン触媒による三連続不斉中心の構築2022

    • Author(s)
      加納太一
    • Organizer
      新学術領域「ハイブリッド触媒」第5回公開シンポジウム
    • Related Report
      2020 Annual Research Report
  • [Presentation] アミン触媒によるアルキニル置換Z-ケチミンの不斉マンニッヒ反応および不斉共役付加反応の開発2021

    • Author(s)
      本間千裕、加納太一、丸岡啓二
    • Organizer
      第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 新規臭素化剤の開発とアミン触媒によるアルデヒドのα-不斉臭素化反応への応用2020

    • Author(s)
      武島愛夏、下垣実央、加納太一、丸岡啓二
    • Organizer
      第49回 複素環化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] キラル相間移動触媒を用いたラクタムの不斉アルキル化による不斉四級炭素の構築2019

    • Author(s)
      犬飼 倫聡・加納 太一・丸岡 啓二
    • Organizer
      日本化学会春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 新規光学活性アミノスルホンアミド触媒の開発と応用2019

    • Author(s)
      武島 愛夏・加納 太一・丸岡 啓二
    • Organizer
      日本化学会春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Enantioselective Mannich Reaction of Z-Ketimines using a Secondary Amine Catalyst2019

    • Author(s)
      HOMMA, Chihiro; MARUYAMA, Hiroki; KANO, Taichi; MARUOKA, Keiji
    • Organizer
      日本化学会春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Lewis acid-catalyzed Petasis-type reaction between in-situ generated N-Boc-protected imines and alkynyl boronate esters2019

    • Author(s)
      YASUMOTO, Kento; KANO, Taichi; MARUOKA, Keiji
    • Organizer
      日本化学会春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 硫黄-炭素結合形成による環状スルホキシイミンの合成2019

    • Author(s)
      前田 祥明・青田 雄介・加納 太一・丸岡 啓二
    • Organizer
      日本化学会春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] スルフィンアミドの硫黄選択的アルキル化によるスルホキシイミンの不斉合成法の開発2019

    • Author(s)
      青田 雄介・加納 太一・丸岡 啓二
    • Organizer
      日本化学会春季年会
    • Related Report
      2019 Annual Research Report

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Published: 2018-04-23   Modified: 2024-01-30  

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