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Eco-friendly enantioselective synthesis using a chiral Si complex

Research Project

Project/Area Number 18K14221
Research Category

Grant-in-Aid for Early-Career Scientists

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

Principal Investigator

Kondo Masaru  大阪大学, 産業科学研究所, 助教 (10816846)

Project Period (FY) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2020: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000)
Fiscal Year 2019: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2018: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Keywords不斉合成 / ケイ素 / ルイス酸 / 有機分子触媒 / インダゾール / スピロオキシインドール / クラウンエーテル / ブレンステッド酸 / BINOL / 不斉触媒 / ルイス酸・塩基 / ホウ素 / グリーンケミストリー
Outline of Final Research Achievements

Chiral Si complexes and organocatalysts were synthesized using easily available chiral BINOL, cinchona alkaloid, and Si reagent to achieve enantioselective reactions. Using these catalysts, enantioselective Pictet-Spengler reaction, hydrosilylation, and cyanation were tested. I found that a chiral crown ether containing Si is effective as a chiral catalyst. During these researches, some works were published (efficient synthesis of 2H-indazoles, practical synthesis of spirooxindoles, and development of azo-crown ether BINOL catalyst).

Academic Significance and Societal Importance of the Research Achievements

ケイ素触媒は安定性と反応性の両立が困難であり、これまで不斉触媒としてほとんど応用例が無かったものの、本研究を通して様々な知見が得られたため、学術的意義はある。また、本研究の過程で得られた研究成果である2H-インダゾールやスピロオキシインドール類の効率的合成においては、医薬資源の合成にも成功しており、社会的意義もある。

Report

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

    (15 results)

All 2021 2020 2019 Other

All Journal Article (4 results) (of which Peer Reviewed: 4 results) Presentation (10 results) (of which Int'l Joint Research: 3 results) Remarks (1 results)

  • [Journal Article] Photoswitchable Chiral Phase Transfer Catalyst2021

    • Author(s)
      Kondo Masaru, Nakamura Kento, Chandu G. Krishnan, Takizawa Shinobu, Abe Tsukasa, Sasai Hiroaki
    • Journal Title

      ACS Catalysis

      Volume: 11 Issue: 3 Pages: 1863-1867

    • DOI

      10.1021/acscatal.1c00057

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Practical Stereoselective Synthesis of C3‐Spirooxindole‐ and C2‐Spiropseudoindoxyl‐Pyrrolidines via Organocatalyzed Pictet‐Spengler Reaction/Oxidative Rearrangement Sequence2021

    • Author(s)
      Kondo Masaru、Matsuyama Naoki、Aye Tin Z.、Mattan Irshad、Sato Tomoyuki、Makita Yoshinori、Ishibashi Masami、Arai Midori A.、Takizawa Shinobu、Sasai Hiroaki
    • Journal Title

      Advanced Synthesis & Catalysis

      Volume: 363 Issue: 10 Pages: 1-17

    • DOI

      10.1002/adsc.202001472

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Exploration of flow reaction conditions using machine-learning for enantioselective organocatalyzed Rauhut-Currier and [3+2] annulation sequence2020

    • Author(s)
      Kondo Masaru、Wathsala H. D. P.、Sako Makoto、Hanatani Yutaro、Ishikawa Kazunori、Hara Satoshi、Takaai Takayuki、Washio Takashi、Takizawa Shinobu、Sasai Hiroaki
    • Journal Title

      Chemical Communications

      Volume: 56 Issue: 8 Pages: 1259-1262

    • DOI

      10.1039/c9cc08526b

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Journal Article] Room‐Temperature, Metal‐Free, and One‐Pot Preparation of 2H‐Indazoles through a Mills Reaction and Cyclization Sequence2019

    • Author(s)
      Kondo Masaru、Takizawa Shinobu、Jiang Yuzhao、Sasai Hiroaki
    • Journal Title

      Chemistry - A European Journal

      Volume: 25 Issue: 42 Pages: 9866-9869

    • DOI

      10.1002/chem.201902242

    • Related Report
      2019 Research-status Report
    • Peer Reviewed
  • [Presentation] 光応答型不斉相間移動触媒の開発2021

    • Author(s)
      中村顕斗, 近藤健, Chandu G. Krishnan, 滝澤忍, 笹井宏明
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Enantioselective Synthesis of Spirooxindoles via Sequential Reactions2021

    • Author(s)
      Tin Zar Aye, Naoki Matsuyama, Irshad Mattan, Masaru Kondo, Shinobu Takizawa, Hiroaki Sasai
    • Organizer
      日本化学会 第101春季年会
    • Related Report
      2020 Annual Research Report
  • [Presentation] Development of Dithienylethene Based Photoswitchable Chiral Catalyst2020

    • Author(s)
      Osamu Yasuda, Yoshitomo Wakabayashi, Masaru Kondo, Hiroaki Sasai
    • Organizer
      Molecular Chirality Asia 2020
    • Related Report
      2020 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 機械学習を活用する精密フロー不斉合成の最適条件探索2020

    • Author(s)
      近藤健, H. D. P. Wathsala, 佐古真, 花谷優太朗, 石川一宣, 原聡, 鷹合孝之, 鷲尾隆, 滝澤忍, 笹井宏明
    • Organizer
      第117回有機合成シンポジウム
    • Related Report
      2020 Annual Research Report
  • [Presentation] Development of a Novel Photoisomerizable Organocatalyst2019

    • Author(s)
      近藤健、中村顕斗、若林良知、笹井宏明
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] Development of Photoresponsive Chiral Pyridine-Oxazoline Ligand2019

    • Author(s)
      中村顕斗、若林良知、近藤健、笹井宏明
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] Development of Asymmetric Catalyst Bearing Dithienylethene and Application2019

    • Author(s)
      若林良知、中村顕斗、近藤健、笹井宏明
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Research-status Report
  • [Presentation] Efficient Prediction of Flow Reaction Conditions Using Machine-Learning for Enantioselective Domino Reaction2019

    • Author(s)
      Kondo Masaru、Wathsala H. D. P.、Sako Makoto、Hanatani Yutaro、Ishikawa Kazunori、Hara Satoshi、Takaai Takayuki、Washio Takashi、Takizawa Shinobu、Sasai Hiroaki
    • Organizer
      13th International CeBiTec Symposium - Multi-Step Syntheses in Biology & Chemistry, An International Young Investigator Conference
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Room-Temperature, Metal-Free and One-Pot Preparation of 2H-indazoles via a Mills Reaction and Cyclization Sequence2019

    • Author(s)
      Kondo Masaru、Takizawa Shinobu、Jiang Yuzhao、Sasai Hiroaki
    • Organizer
      27th International Society of Heterocyclic Chemistry Congress
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] Development of Novel Photoswitchable Chiral Catalyst2019

    • Author(s)
      近藤健、中村顕斗、笹井宏明
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Remarks] 産業科学研究所 笹井研究室 学会発表

    • URL

      https://www.sanken.osaka-u.ac.jp/labs/soc/socmain.html

    • Related Report
      2018 Research-status Report

URL: 

Published: 2018-04-23   Modified: 2022-01-27  

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