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Studies of Dynamic Stereochemical Behavior of Benzodiheterole-containing Heterohelicenes and Their Application

Research Project

Project/Area Number 18K14224
Research Category

Grant-in-Aid for Early-Career Scientists

Allocation TypeMulti-year Fund
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionKumamoto University

Principal Investigator

Arae Sachie  熊本大学, 大学院先端科学研究部(理), 助教 (90754896)

Project Period (FY) 2018-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2020: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2019: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000)
Fiscal Year 2018: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywordsヘテロヘリセン / 螺旋不斉 / 動的速度論分割 / σ-ヘテロアリール錯体 / パラジウム錯体 / 白金錯体 / シス-トランス異性化 / フェロセン / 面不斉 / 環化脱水素化 / ヘリセン / 立体化学挙動 / 不斉合成
Outline of Final Research Achievements

In this research, we aimed at development of a new efficient synthetic approach to heterohelicenes based on dynamic kinetic resolution.
We developed a new synthetic route to benzodiheterole-containing heterohelicenes and their highly regioselective peripheral modification. Kinetic analyses revealed that the stereochemical stability of the heterohelicenes thus obtained were highly dependent on the substituent. Based on these results, we achieved dynamic kinetic resolution of heterohelicenes with chiral catalyst.

Academic Significance and Societal Importance of the Research Achievements

従来、ヘテロヘリセン合成は、もっぱら「分子歪みが大きくラセミ化しない」ものを標的とし、「分子歪みの小さいアキラルな非環式基質」を環化させる方法をとっていた。しかし、この手法は、分子歪みの上昇に打ち勝つために高い反応温度など厳しい環化反応条件を必要とするため、立体化学制御が極めて難しいという課題があった。これに対して本手法は、分子歪みが中程度の「動的」ヘテロヘリセンの置換反応によって、分子歪みが増大した「準静的」ヘテロヘリセンを得るというものである。このように、これまでにないヘテロヘリセン類の不斉合成手法の開発に取り組んだものであるという点で、本研究は学術的意義がある。

Report

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

    (12 results)

All 2021 2019 2018

All Presentation (12 results) (of which Int'l Joint Research: 4 results)

  • [Presentation] Preparation and Reactivity of Air-stable Palladium(II)-(σ-heteroaryl) Complexes via Hydropalladation of o-Alkynylnaphthol Derivatives2021

    • Author(s)
      Sachie Arae, Ryo Irie
    • Organizer
      第67回有機金属化学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] o-アルキニルナフトール誘導体の分子内ヒドロパラジウム化による空気中で安定なパラジウム(II)-(σ-ヘテロアリール)錯体の合成2021

    • Author(s)
      荒江 祥永,入江 亮
    • Organizer
      日本化学会第101春季年会
    • Related Report
      2020 Research-status Report
  • [Presentation] Synthesis and Dynamic Stereochemical Behavior of Benzodiheterole-containing Hetero[6]- and [7]helicenes2019

    • Author(s)
      Sachie Arae, Takaaki Mori, Nobutsugu Hamamoto, Michinori Sumimoto, Hitoshi Fujimoto, Kazunobu Igawa, Katsuhiko Tomooka, Ryo Irie
    • Organizer
      The 29th International Symposium on Chirality
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Regio- and Stereoselective Intramolecular Cyclization Reactions of Benzoheteroles and Alkynes through the Formation of Vinylidene ortho-Quinone Methide Intermediates2019

    • Author(s)
      Sachie Arae, Shota Beppu, Kazunobu Igawa, Katsuhiko Tomooka, Ryo Irie
    • Organizer
      The 27th International Society of Heterocyclic Chemistry Congress
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] ベンゾジヘテロール骨格を有するアザオキサ[6]ヘリセン類の合成と立体化学挙動に関する研究2019

    • Author(s)
      荒江 祥永, 今里 大志, 森 崇彰, 井川 和宣, 友岡 克彦, 入江 亮
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] Highly Regioselective Postmodification of Benzodiheterole-based Heterohelicenes and Substituent Effects on Their Stereochemical Behavior2018

    • Author(s)
      S. Arae, R. Kobayashi, T. Imazato, T. Mori, N. Hamamoto, H. Fujimoto, K. Igawa, K. Tomooka, R. Irie
    • Organizer
      6the Japan-UK Symposium on Asymmetric Catalysis
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] ジオキサ[7]ヘリセンの合成および高位置選択的な直接誘導化2018

    • Author(s)
      荒江 祥永,小林 稜, 片岡 天明, 井川 和宣, 友岡 克彦, 入江 亮
    • Organizer
      第44回 反応と合成の進歩シンポジウム
    • Related Report
      2018 Research-status Report
  • [Presentation] Efficient Synthesis and Highly Site-selective Post-functionalization of Benzodiheterole-containing Heterohelicenes2018

    • Author(s)
      S. Arae, R. Kobayashi, T. Kataoka, K. Igawa, K. Tomooka, R. Irie
    • Organizer
      The 14th International Kyoto Conference on New Aspects of Organic Chemistry
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Efficient Synthesis of a Variety of Oxa[7]helicenes based on Highly Regioselective Post-transformation2018

    • Author(s)
      S. Arae, R. Kobayashi, T. Kataoka, K. Igawa, K. Tomooka, R. Irie
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] ベンゾジヘテロール骨格を基盤とするヘテロ[7]ヘリセン類の合成,高位置選択的外縁部修飾, および立体化学的特性2018

    • Author(s)
      荒江 祥永, 小林 稜, 片岡 天明, 濱本 信次, 藤本 斉, 井川 和宣, 友岡 克彦, 入江 亮
    • Organizer
      第48回複素環化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] フロインドール骨格を含むヘテロ[6]ヘリセン類の合成および動的立体化学挙動2018

    • Author(s)
      荒江 祥永, 今里 大志, 森 崇彰, 井川 和宣, 友岡 克彦, 入江 亮
    • Organizer
      第48回複素環化学討論会
    • Related Report
      2018 Research-status Report
  • [Presentation] Regioselective Direct Functionalization of Heterohelicenes and Their Stereochemical Behavior2018

    • Author(s)
      S. Arae, R. Kobayashi, T. Kataoka, N. Hamamoto, H. Fujimoto, K. Igawa, K. Tomooka, R. Irie
    • Organizer
      Molecular Chirality 2018
    • Related Report
      2018 Research-status Report

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Published: 2018-04-23   Modified: 2023-01-30  

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