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Development of Asymmetric Reactions Based on Donor·Acceptor Bifunctional Catalyst Concept

Research Project

Project/Area Number 16H02274
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionNagoya University

Principal Investigator

Kitamura Masato  名古屋大学, 創薬科学研究科, 教授 (50169885)

Project Period (FY) 2016-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥45,760,000 (Direct Cost: ¥35,200,000、Indirect Cost: ¥10,560,000)
Fiscal Year 2020: ¥8,970,000 (Direct Cost: ¥6,900,000、Indirect Cost: ¥2,070,000)
Fiscal Year 2019: ¥8,970,000 (Direct Cost: ¥6,900,000、Indirect Cost: ¥2,070,000)
Fiscal Year 2018: ¥8,970,000 (Direct Cost: ¥6,900,000、Indirect Cost: ¥2,070,000)
Fiscal Year 2017: ¥8,970,000 (Direct Cost: ¥6,900,000、Indirect Cost: ¥2,070,000)
Fiscal Year 2016: ¥9,880,000 (Direct Cost: ¥7,600,000、Indirect Cost: ¥2,280,000)
Keywords不斉触媒反応 / 二官能性触媒 / 反応機構解明 / 不斉合成 / 脱水型アリル化 / 機構解明研究 / 分子触媒 / 水素化 / アリル化 / ルテニウム / 不斉触媒 / スフィンゴシン / 触媒反応
Outline of Final Research Achievements

Recently, we have developed a new dehydrative allylation/deallylation catalyst, quinaldic acid (QAH)-CpRu, which improves the usefulness of allylic protecting groups. From this catalysis as a starting point, we have developed a soft Lewis acid/hard Bronsted acid-combined catalyst consisting of a new optically active picolinic acid-type ligand as well as a CpRu complex with a new chiral sp2 nitrogen-based bidentate ligand, combined with a Bronsted acid. These catalysts enabled new Tsuji-Trost (T-T)-type reaction with dehydrative manner. In this work, these two catalytic systems were thoroughly extended to substrate applicability and mechanistic studies were carried out for the estimation of reaction pathways and the origin of the reactive enantioselectivity.

Academic Significance and Societal Importance of the Research Achievements

Tsuji-Trost型反応は、様々な有用生理活性物質の合成を可能とし,まさに有機合成の確たる基盤の一角をなしている。我々が開発した二つの触媒系は、アリルアルコールを直接に用いて、様々なプロトン性求核剤を脱水的にアリル化できる初めての例である。共生成物は「水」だけなので、生成物単離の操作性も高く、持続性社会の実現の一角をなすと期待される。弱酸性条件を用いる反応の特性は,従来法では不可能であった様々な反応形態を実現する可能性を秘める。本手法の有用性をさらに高める本研究課題の社会的意義は極めて高い。

Report

(6 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • 2017 Annual Research Report
  • 2016 Annual Research Report
  • Research Products

    (36 results)

All 2021 2020 2019 2018 2017 2016

All Journal Article (19 results) (of which Int'l Joint Research: 5 results,  Peer Reviewed: 19 results,  Open Access: 5 results) Presentation (17 results) (of which Int'l Joint Research: 2 results,  Invited: 7 results)

  • [Journal Article] A Monocationic Zn(II) Acetate Complex of a Chiral Bisamidine Dioxolane Ligand, Naph-diPIM-dioxo-R, for the Asymmetric 1,3-Dipolar Cycloaddition of Tridentate α-Substituted α-Imino Esters and Acrylates to Multi-Substituted Prolines: Importance of an n-π* Interaction for High Enantioselectivity2021

    • Author(s)
      Kiran Indukuru Naga Chaithanya、Fujita Kazuki、Kobayashi Kazuki、Tanaka Shinji、Kitamura Masato
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 94 Issue: 1 Pages: 295-308

    • DOI

      10.1246/bcsj.20200266

    • NAID

      130007968776

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Mechanism of the Asymmetric Dehydrative Allylative Cyclization of Alcohols to Cyclic Ethers Catalyzed by a CpRu Complex of the Chiral Picolinic Acid-Type Ligand, Cl-Naph-PyCOOH: Is a π-Allyl Intermediate Present?2021

    • Author(s)
      Suzuki Yusuke、Iwase Shoutaro、Ratanasak Manussada、Hasegawa Jun-ya、Tanaka Shinji、Kitamura Masato
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 94 Issue: 2 Pages: 440-450

    • DOI

      10.1246/bcsj.20200228

    • NAID

      130007995431

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Mechanism Change of (+)-Nonlinear Effect in a Phase Separation System in a CuII-Catalyzed Asymmetric Friedel-Crafts Reaction Using a C2-Chiral Dioxolane-Containing-Bisamidine Ligand, Naph-diPIM-dioxo-iPr2020

    • Author(s)
      Le Thien Phuc、Tanaka Shinji、Yoshimura Masahiro、Kitamura Masato
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 93 Issue: 11 Pages: 1319-1333

    • DOI

      10.1246/bcsj.20200172

    • NAID

      130007939768

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Asymmetric Synthesis of Multi‐substituted Prolines via a Catalytic 1,3‐Dipolar Cycloaddition Using a Monocationic Zn II OAc Complex of a Chiral Bisamidine Ligand, Naph‐diPIM‐dioxo‐R2020

    • Author(s)
      Chaithanya Kiran I. N.、Fujita Kazuki、Tanaka Shinji、Kitamura Masato
    • Journal Title

      ChemCatChem

      Volume: 12 Issue: 22 Pages: 5613-5617

    • DOI

      10.1002/cctc.202001202

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] CpRuII-chiral bisamidine complex catalyzed asymmetric Carroll-type decarboxylative allylation of β-keto allyl esters2020

    • Author(s)
      Ogawa Shintarou、Miyata Kengo、Kawakami Sho、Tanaka Shinji、Kitamura Masato
    • Journal Title

      Tetrahedron

      Volume: 76 Issue: 7 Pages: 130888-130888

    • DOI

      10.1016/j.tet.2019.130888

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] CpRu/Bronsted Acid-Catalyzed Enantioselective Dehydrative Cyclization of Pyrroles N-Tethered with Allylic Alcohols2020

    • Author(s)
      Iwase Shoutaro、Suzuki Yusuke、Tanaka Shinji、Kitamura Masato
    • Journal Title

      Organic Letters

      Volume: 22 Issue: 5 Pages: 1929-1933

    • DOI

      10.1021/acs.orglett.0c00290

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] A Chiral Picolinic Acid Ligand, Cl-Naph-PyCOOH, for CpRu-Catalyzed Dehydrative Allylation: Design, Synthesis, and Properties2019

    • Author(s)
      Tanaka Shinji、Suzuki Yusuke、Kimura Takahiro、Kitamura Masato
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 92 Issue: 10 Pages: 1707-1720

    • DOI

      10.1246/bcsj.20190134

    • NAID

      130007728635

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Water, an Essential Element for a ZnII‐Catalyzed Asymmetric Quinone Diels‐Alder Reaction: Multi‐Selective Construction of Highly Functionalized cis‐Decalins2019

    • Author(s)
      Morimoto Kyosuke、Le Thien Phuc、Manna Sudipta Kumar、Kiran I. N. Chaithanya、Tanaka Shinji、Kitamura Masato
    • Journal Title

      Chemistry - An Asian Journal

      Volume: 14 Issue: 19 Pages: 3283-3290

    • DOI

      10.1002/asia.201900995

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis of the core structure of phalarine2019

    • Author(s)
      Douki Kazuya、Shimokawa Jun、Kitamura Masato
    • Journal Title

      Organic & Biomolecular Chemistry

      Volume: 17 Issue: 7 Pages: 1727-1730

    • DOI

      10.1039/c8ob02320d

    • Related Report
      2019 Annual Research Report 2018 Annual Research Report 2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Short and Atom-Economic Enantioselective Synthesis of the σ1-Receptor Ligands (S)- and (R)-Fluspidine-Important Tools for Positron Emission Tomography Studies2019

    • Author(s)
      Bunse Paul、Schlepphorst Christoph、Glorius Frank、Kitamura Masato、W?nsch Bernhard
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 84 Issue: 21 Pages: 13744-13754

    • DOI

      10.1021/acs.joc.9b01882

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Rapid Entry into Biologically Relevant α,α-Difluoroalkylphosphonates Bearing Allyl Protection-Deblocking under Ru(II)/(IV)-Catalysis2019

    • Author(s)
      Panigrahi Kaushik、Fei Xiang、Kitamura Masato、Berkowitz David B.
    • Journal Title

      Organic Letters

      Volume: 21 Issue: 24 Pages: 9846-9851

    • DOI

      10.1021/acs.orglett.9b03707

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Bisamidine-Cu(I)-catalyzed C-Allylation of 1,3-Dicarbonyl Compounds with Simple Cyclic Alkenes Using Di-tert-butyl Peroxide2018

    • Author(s)
      Tanaka Shinji、Ramachandran Gunasekar、Hori Yohei、Kitamura Masato
    • Journal Title

      Chemistry Letters

      Volume: 47 Issue: 12 Pages: 1486-1489

    • DOI

      10.1246/cl.180741

    • NAID

      130007534810

    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Revisiting the CuII-Catalyzed Asymmetric Friedel-Crafts Reaction of Indole with Trifluoropyruvate2018

    • Author(s)
      Le Thien Phuc、Higashita Kazuyuki、Tanaka Shinji、Yoshimura Masahiro、Kitamura Masato
    • Journal Title

      Organic Letters

      Volume: 20 Issue: 22 Pages: 7149-7153

    • DOI

      10.1021/acs.orglett.8b03086

    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Mechanistic Study of the Ru-Catalyzed Asymmetric Hydrogenation of Nonchelatable and Chelatable tert-Alkyl Ketones Using the Linear Tridentate sp3P/sp3NH/sp2N-Combined Ligand PN(H)N: RuNH- and RuNK-Involved Dual Catalytic Cycle2018

    • Author(s)
      Nakane Satoshi、Yamamura Tomoya、Manna Sudipta Kumar、Tanaka Shinji、Kitamura Masato
    • Journal Title

      ACS Catalysis

      Volume: 8 Issue: 12 Pages: 11059-11075

    • DOI

      10.1021/acscatal.8b02671

    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Synthesis of fluspidine via asymmetric NaBH4 reduction of silicon enolates of β-keto esters2018

    • Author(s)
      Nakane Satoshi、Yoshinaka Sho、Iwase Shoutaro、Shuto Yoshihiro、Bunse Paul、Wuensch Bernhard、Tanaka Shinji、Kitamura Masato
    • Journal Title

      Tetrahedron

      Volume: 74 Issue: 38 Pages: 5069-5084

    • DOI

      10.1016/j.tet.2018.04.005

    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Enantio- and Diastereoselective Dehydrative “One-Step” Construction of Spirocarbocycles via a Ru/H+-Catalyzed Tsuji-Trost Approach2017

    • Author(s)
      Yusuke Suzuki, Namdev Vatmurge, Shinji Tanaka, Masato Kitamura
    • Journal Title

      Chemistry - An Asian Journal

      Volume: 12 Issue: 6 Pages: 633-637

    • DOI

      10.1002/asia.201700013

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Development of an Axially Chiral sp3P/sp3NH/sp2N-Combined Linear Tridentate Ligand―fac-Selective Formation of Ru(II) Complexes and Application to Ketone Hydrogenation
2016

    • Author(s)
      Tomoya Yamamura, Satoshi Nakane, Yuko Nomura, Shinji Tanaka, Masato Kitamura*
    • Journal Title

      Tetrahedron

      Volume: 未定 Issue: 26 Pages: 3781-3789

    • DOI

      10.1016/j.tet.2016.02.007

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Development of a Divergent Synthetic Route to the Erythrina Alkaloids: Asymmetric Syntheses of 8-Oxo-erythrinine, Crystamidine, 8-Oxo-erythraline, and Erythraline2016

    • Author(s)
      Hirotatsu Umihara, Tomomi Yoshino, Jun Shimokawa, Masato Kitamura, Tohru Fukuyama
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 55 Issue: 24 Pages: 6915-6918

    • DOI

      10.1002/anie.201602650

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Total Synthesis of (+)-Hinckdentine A via a Catalytic Dearomatization Approach2016

    • Author(s)
      Kazuya Douki, Hiroyuki Ono, Tohru Taniguchi, Jun Shimokawa, Masato Kitamura, Tohru Fukuyama
    • Journal Title

      Journal of the American Chemical Society

      Volume: 138 Issue: 44 Pages: 14578-14581

    • DOI

      10.1021/jacs.6b10237

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed
  • [Presentation] Mechanistic Study on Intramolecular Asymmetric Dehydrative Allylation of Alcohols Catalyzed by CpRu Complex of Chiral 2-Pyridinecarboxylic Acid Ligand2019

    • Author(s)
      田中慎二, 鈴木悠介, 岩瀬翔太郎, 北村雅人
    • Organizer
      20th Tetrahedron Symposium
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] CpRu-catalyzed Enantioselective Dehydrative Cyclization of Protic Nucleophile tethered Allylic Alcohols -From Allyl Protecting Group Chemistry to Tsuji-Trost-type Allylation-2019

    • Author(s)
      北村雅人
    • Organizer
      27th International Society of Heterocyclic Chemistry Congress
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Mechanistic Insight into fac-PN(H)N-Ru Catalyzed Asymmetric Hydrogenation of tert-Alkyl Ketones2019

    • Author(s)
      中根智志, 田中慎二, 北村雅人
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 辻-トロスト反応の新展開2019

    • Author(s)
      北村雅人
    • Organizer
      岡山大学大学院自然科学研究科講演会
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] 辻-トロスト反応の新展開2019

    • Author(s)
      北村雅人
    • Organizer
      北海道大学大学院工学研究院講演会
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] 環境負荷低減型「触媒的不斉辻・トロスト反応」の開発に向けて2019

    • Author(s)
      北村雅人
    • Organizer
      第2回グリーン合成&触媒 名古屋シンポジウム
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] 脱水型触媒的不斉 Tsuji-Trost 反応の機構解明研究2019

    • Author(s)
      北村雅人
    • Organizer
      新学術領域研究「精密制御反応場」 第6回公開シンポジウム
    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
  • [Presentation] Dehydrative Tsuji-Trost-type Allylation Using CpRu/Broensted Acid Combined Catalyst: Mechanism2019

    • Author(s)
      北村雅人
    • Organizer
      The 8th Kansai-CMDS Meeting on OMCOS at Seoul
    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
  • [Presentation] PNN-Ru-DMSO錯体を触媒に用いるケトン類の不斉水素化の機構2018

    • Author(s)
      北村雅人
    • Organizer
      新学術領域研究「精密制御反応場」 第4回公開シンポジウム
    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
  • [Presentation] Donor-Acceptor Bifunctional Catalyst ―From DAIB-Zn to Ru/Broensted Acid Combined Catalyst―2018

    • Author(s)
      北村雅人
    • Organizer
      International Symposium on Pure&Applied Chemistry 2018
    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
  • [Presentation] ドナー・アクセプター二官能性触媒の開発2018

    • Author(s)
      北村雅人
    • Organizer
      京都大学大学院理学研究科有機合成化学研究室 大学院講義
    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
  • [Presentation] Chemistry In JAPAN2018

    • Author(s)
      北村雅人
    • Organizer
      Islom Karimov Nomidagi Toshkent Davlat Texnika Universiteti
    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
  • [Presentation] Donor-Acceptor Bifunctional Catalyst ―From DAIB-Zn to Ru/Broensted Acid Combined Catalyst―2018

    • Author(s)
      北村雅人
    • Organizer
      Bristol-Myers Squibb講演会
    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
  • [Presentation] Donor-Acceptor Bifunctional Catalyst ―From DAIB-Zn to Ru/Broensted Acid Combined Catalyst―2018

    • Author(s)
      北村雅人
    • Organizer
      Columbia University 講演会
    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
  • [Presentation] ビスアミジン型sp2N系二座配位子の開発2016

    • Author(s)
      北村雅人
    • Organizer
      講演会(
    • Place of Presentation
      東京工業大学
    • Year and Date
      2016-09-19
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] ヒンクデンチンAの不斉全合成2016

    • Author(s)
      道木和也、小野裕之、下川 淳、福山 透、北村雅人
    • Organizer
      第58回天然有機化合物討論会
    • Place of Presentation
      東北大学
    • Year and Date
      2016-09-14
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] アリル化・脱アリル化―ルテニウム/ブレンステッド酸 混合触媒―2016

    • Author(s)
      北村雅人
    • Organizer
      講演会「有機金属化学の大潮流」
    • Place of Presentation
      分子科学研究所
    • Year and Date
      2016-09-02
    • Related Report
      2016 Annual Research Report
    • Invited

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Published: 2016-04-21   Modified: 2022-01-27  

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