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Design and Synthesis of Dynamic Planar Chiral Medium-sized Cyclic Molecule

Research Project

Project/Area Number 16H04113
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKyushu University

Principal Investigator

Tomooka Katsuhiko  九州大学, 先導物質化学研究所, 教授 (70207629)

Research Collaborator Igawa Kazunobu  
Kawasaki Yuuya  
Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥17,290,000 (Direct Cost: ¥13,300,000、Indirect Cost: ¥3,990,000)
Fiscal Year 2018: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2017: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2016: ¥9,490,000 (Direct Cost: ¥7,300,000、Indirect Cost: ¥2,190,000)
Keywords有機合成化学 / 分子キラリティー / 動的面不斉分子 / 機能性キラル分子 / 不斉合成
Outline of Final Research Achievements

We performed systematic study on dynamic planar chiral heterocycles: nine-membered E,Z-diallylic heterocycles and [7]-orthocyclphenes, and found that their stereochemical stabilities are highly dependent on substituent on the E-alkene, embedded heteroatom X in the ring, and ring size. Also we have found that stereochemical stability of the planar chiral molecules can be controlled by addition of Lewis acid. Furthermore, we have developed dynamic asymmetric induction method which provides enantioenriched forms of the planar chiral molecules.

Academic Significance and Societal Importance of the Research Achievements

キラル分子の研究は化学の基礎や生命現象の本質を理解するために重要である.その主たる対象は炭素中心性不斉を有するキラル分子であった.これに対して本研究では,我々が先に見出した動的面不斉を有する中員環分子という新規なキラル分子を対象として系統的な研究を行い,その学理を探求した.また,その立体化学を外的キラル因子の影響で変化させて制御する動的不斉誘起法の開発に成功した.

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Annual Research Report
  • 2016 Annual Research Report
  • Research Products

    (42 results)

All 2019 2018 2017 2016

All Journal Article (6 results) (of which Peer Reviewed: 6 results,  Open Access: 1 results,  Acknowledgement Compliant: 2 results) Presentation (35 results) (of which Int'l Joint Research: 9 results,  Invited: 11 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Synthesis and Stereochemical Analysis of Dynamic Planar Chiral Nine-membered Diallylic Amide: Significant Substituent Effect on Stereochemical Stability2019

    • Author(s)
      Hayashi, J.; Uehara, K.; Ano, Y.; Kawasaki, Y.; Igawa, K.; Tomooka, K.
    • Journal Title

      Heterocycles

      Volume: 印刷中

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Preparation of Enantioenriched Chiral Organic Molecules by Dynamic Asymmetric Induction from Outer Chiral Source2019

    • Author(s)
      Igawa, K.; Kawasaki, Y.; Ano, Y.; Kashiwagi, T.; Ogawa, K.; Hayashi, J.; Morita, R.; Yoshioka, Y.; Kazuhiro, U.; Tomooka, K.
    • Journal Title

      Chemistry Letters

      Volume: 48

    • NAID

      130007674910

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Efficient Approach to Medium-sized Cyclic Molecules Containing (E)-Alkene via Z to E Photochemical Isomerization in the Presence of AgNO3-impregnated Silica Gel2018

    • Author(s)
      Machida, K.; Yoshida, Y.; Igawa, K.; Tomooka, K.
    • Journal Title

      Chemistry Letters

      Volume: 47 Issue: 2 Pages: 186-188

    • DOI

      10.1246/cl.170937

    • NAID

      130006337725

    • Related Report
      2018 Annual Research Report 2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Chemistry of Planar Chiral Medium-sized Heterocycles2017

    • Author(s)
      友岡 克彦
    • Journal Title

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 75 Issue: 5 Pages: 449-457

    • DOI

      10.5059/yukigoseikyokaishi.75.449

    • NAID

      130006903192

    • ISSN
      0037-9980, 1883-6526
    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Chemistry of Planar Chiral Medium-sized Heterocycles2017

    • Author(s)
      Tomooka, K.
    • Journal Title

      J. Synth. Org. Chem. Jpn.

      Volume: 75

    • NAID

      130006903192

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis and Stereochemical Analysis of Planar-Chiral (E)-4-[7]Orthocyclophene2016

    • Author(s)
      Igawa, K.; Machida, K.; Noguchi, K.; Uehara, K.; Tomooka, K.
    • Journal Title

      J. Org. Chem.

      Volume: 81 Issue: 23 Pages: 11587-11593

    • DOI

      10.1021/acs.joc.6b01799

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] 非天然型キラル分子の化学2018

    • Author(s)
      友岡克彦
    • Organizer
      モレキュラー・キラリティー2018
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] アルケンの光異性化を鍵とする面不斉中員環分子の効率的合成2018

    • Author(s)
      吉田祐樹,町田康平,岡本真梨子,阿野勇介,井川和宣,友岡克彦
    • Organizer
      第28回万有福岡シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] (E)-4-[7]オルトシクロフェンの合成と立体化学2018

    • Author(s)
      井川和宣,町田康平,吉田祐樹,野口恭平,上原和浩,友岡克彦
    • Organizer
      第113回有機合成シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] アルケンの光異性化を鍵とする面不斉中員環分子の合成2018

    • Author(s)
      吉田祐樹,町田康平,井川和宣,友岡克彦
    • Organizer
      統合物質創製化学研究推進機構 第4回国内シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] 動的面不斉を有する10員環ジアリルアミドの設計と合成2018

    • Author(s)
      林純一,堀川真太郎,井川和宣,友岡克彦
    • Organizer
      統合物質創製化学研究推進機構 第4回国内シンポジウム
    • Related Report
      2018 Annual Research Report
  • [Presentation] Chemistry of Medium-sized Unsaturated Organonitrogen Cycles2018

    • Author(s)
      Katsuhiko Tomooka
    • Organizer
      8th SPANISH-PORTUGUESE-JAPANESE ORGANIC CHEMISTRY SYMPOSIUM
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] パイスター分子制御による未来型分子変換研究拠点 2018年度 公開シンポジウム2018

    • Author(s)
      友岡克彦
    • Organizer
      珍奇なキラル分子
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] Photochemical Isomerization Approach to Planar Chiral Medium-sized Cyclic Molecules2018

    • Author(s)
      Yuki Yoshida, Kouhei Machida, Mariko Okamoto, Yusuke Ano, Kazunobu Igawa, Katsuhiko Tomooka
    • Organizer
      IRCCS 2nd International Symposium
    • Related Report
      2018 Annual Research Report
  • [Presentation] 非天然型キラル分子の化学2018

    • Author(s)
      友岡克彦
    • Organizer
      鳥取大学 GSCセミナー
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] 動的キラルなクロモン誘導体の設計,合成とその応用2018

    • Author(s)
      河崎悠也,井本祐樹,友岡克彦
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 動的キラルな10員環ジアリルアミドの設計と合成2018

    • Author(s)
      林純一,河崎悠也,井川和宣,友岡克彦
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 面不斉を有する4-アザ9員環ラクタムの設計と合成2018

    • Author(s)
      吉田祐樹,井川和宣,友岡克彦
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 10員環ジアリルアミド類の合成とその立体化学挙動2018

    • Author(s)
      林純一,堀川真太郎,井川和宣,友岡克彦
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 6位置換3-アザ[7]オルトピリジノフェンの合成とその立体化学挙動2018

    • Author(s)
      阿野勇介,吉岡由香梨,田中澄怜,河崎悠也,井川和宣,友岡克彦
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 硝酸銀含浸シリカゲル共存下での光異性化を鍵とするE-アルケン中員環分子の効率的合成2018

    • Author(s)
      吉田祐樹,町田康平,井川和宣,友岡克彦
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Chemistry of Medium-sized Unsaturated Heterocycles2018

    • Author(s)
      Tomooka Katsuhiko
    • Organizer
      IRCCS The 1st International Symposium
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 動的キラルなα,β-不飽和ケトンの設計と合成2017

    • Author(s)
      河崎悠也, 牟田口実咲, 井川和宣, 友岡克彦
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾大(神奈川)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] 動的キラルな1,3-ケトアミドエノラートの合成とその変換2017

    • Author(s)
      河崎悠也, 上久保椋, 井川和宣, 友岡克彦
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾大(神奈川)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] 動的キラルな9員環ラクタムの設計,合成とその立体化学挙動2017

    • Author(s)
      阿野勇介, 岡本真梨子, 吉田祐樹, 井川和宣, 友岡克彦
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾大(神奈川)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Annual Research Report
  • [Presentation] 非天然キラル分子の化学2017

    • Author(s)
      友岡克彦
    • Organizer
      京都大学大学院材料化学専攻 特別講演会
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] 面不斉を有する9員環ラクタムの合成とその立体化学挙動の研究2017

    • Author(s)
      吉田祐樹,岡本真梨子,阿野勇介,井川和宣,友岡克彦
    • Organizer
      第29回若手研究者のためのセミナー
    • Related Report
      2017 Annual Research Report
  • [Presentation] 面不斉を有するラクタムの設計と合成2017

    • Author(s)
      阿野勇介,吉田祐樹,岡本真梨子,井川和宣,友岡克彦
    • Organizer
      第4回中分子戦略若手シンポジウム
    • Related Report
      2017 Annual Research Report
  • [Presentation] 面不斉を有する9員環ラクタムの合成とその立体化学挙動の研究2017

    • Author(s)
      阿野勇介,吉田祐樹,岡本真梨子,井川和宣,友岡克彦
    • Organizer
      第54回化学関連支部合同九州大会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Design and Synthesis of Novel Dynamic Planar-Chiral Amide: Stereochemical Effect of C4-Substituent2017

    • Author(s)
      Jun-ichi Hayashi, Yusuke Ano, Kazuhiro Uehara, Kazunobu Igawa, Katsuhiko Tomooka
    • Organizer
      Junior ICCEOCA-7, ARNCEOCA-3
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Chemistry of Unnatural Chiral Molecule2017

    • Author(s)
      Katsuhiko Tomooka
    • Organizer
      2017 Wender Symposium
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Chemistry of Unnatural Chiral Molecule2017

    • Author(s)
      Katsuhiko Tomooka
    • Organizer
      Special Lecture at Shanghai Institute of Materia Medica
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Chemistry of Unnatural Chiral Molecule2017

    • Author(s)
      Katsuhiko Tomooka
    • Organizer
      Special Lecture at Shanghai Institute of Organic Chemistry
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis Utility of Newly Designed Axial Chiral Enolates2016

    • Author(s)
      Yuuya Kawasaki, Ryota Kamikubo, Kazunobu Igawa, Katsuhiko Tomooka
    • Organizer
      JICCEOCA-6
    • Place of Presentation
      九州大学 (福岡)
    • Year and Date
      2016-10-24
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis, Stereochemical Behavior, and Transformation of 3-Aza[7]orthocyclophenes2016

    • Author(s)
      Yusuke Ano, Yukari Yoshioka, Kohei Ogawa Ryouta Morita, Kazunobu Igawa, Katsuhiko Tomooka
    • Organizer
      JICCEOCA-6
    • Place of Presentation
      九州大学 (福岡)
    • Year and Date
      2016-10-24
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 私達は何を間違え,何を見い出したのか2016

    • Author(s)
      友岡克彦
    • Organizer
      第32回若手化学者のための化学道場
    • Place of Presentation
      にぎたつ会館(愛媛)
    • Year and Date
      2016-08-25
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] 軸不斉α,β-不飽和ケトンの設計と合成2016

    • Author(s)
      河崎悠也,牟田口実咲,井川和宣,友岡克彦
    • Organizer
      第32回若手化学者のための化学道場
    • Place of Presentation
      にぎたつ会館(愛媛)
    • Year and Date
      2016-08-25
    • Related Report
      2016 Annual Research Report
  • [Presentation] 面不斉を有する中員環ラクタムの設計と合成2016

    • Author(s)
      阿野勇介, 岡本真梨子, 吉田祐樹,井川和宣,友岡克彦
    • Organizer
      第32回若手化学者のための化学道場
    • Place of Presentation
      にぎたつ会館(愛媛)
    • Year and Date
      2016-08-25
    • Related Report
      2016 Annual Research Report
  • [Presentation] 面不斉中員環アミドの触媒的不斉合成2016

    • Author(s)
      井川和宣,阿野勇介,市川延雅,友岡克彦
    • Organizer
      第109回有機合成シンポジウム
    • Place of Presentation
      東京工業大学(東京)
    • Year and Date
      2016-06-08
    • Related Report
      2016 Annual Research Report
  • [Presentation] Chemistry of Planar Chiral Heterocycles2016

    • Author(s)
      Katsuhiko Tomooka
    • Organizer
      Molecular Chirality Asia 2016
    • Place of Presentation
      Convention Center(大阪)
    • Year and Date
      2016-04-20
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] キラル分子科学の再認識 Recognition of science of chiral molecule 友岡克彦2016

    • Author(s)
      友岡克彦
    • Organizer
      統合物質創製化学研究推進機構シンポジウム
    • Place of Presentation
      名古屋大学(愛知)
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Patent(Industrial Property Rights)] 光学活性体の製造方法、光学活性体、キラル分子の製造方法およびキラル分子2017

    • Inventor(s)
      友岡克彦,井川和宣
    • Industrial Property Rights Holder
      友岡克彦,井川和宣
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2017-097928
    • Filing Date
      2017
    • Related Report
      2017 Annual Research Report

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Published: 2016-04-21   Modified: 2020-03-30  

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