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Development of Synthetic Methods Based on Generation of Low-Valent Titaniums

Research Project

Project/Area Number 17K05869
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionKanagawa University

Principal Investigator

Okamoto Sentaro  神奈川大学, 工学部, 教授 (00201989)

Project Period (FY) 2017-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2019: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2018: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2017: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Keywords低原子価チタン / 精密有機合成 / 環化反応 / 環化付加反応 / McMurryカップリング / 精密合成反応 / 選択的合成 / 低原子価チタニウム
Outline of Final Research Achievements

The purposes are development of novel methods for generating new low-valent titanium species and their use for developing new synthetic reactions and catalyses. Synthesis of novel vitamin D derivatives by using highly stereoselective cyclization of enyne substrates mediated by the divalent-titanium and their binding ability to the human vitamin D receptor protein were accomplished. In addition, the titanacyclopentene intermediates derived from enyne substrates and the divalent-titanium could react with bis-electronic reagent such as ethyl formate to undergo bicyclizaiton reaction affording bicyclic cyclopentenol derivatives. A new dual-mode polymerization method was also developed, in which a Ti(O-i-Pr)4/Me3SiCl/Mg reagent simultaneously promoted McMurry coupling of dialdehydes and cyclotrimerization of aldehyde-alkynes in one-flask and the reaction gave branched polymers. CpTiCl3/Mg/Me3SiCl reagents were developed as new low-valent titanium catalyst for alkyne [2+2+2] cycloaddition.

Academic Significance and Societal Importance of the Research Achievements

低原子価チタン反応剤について,二価チタン等価反応剤の高度利用の事例を示したことでこの反応剤のより広範囲での利用を促進し,有機合成化学分野に寄与できるものと考えられる。また,新たな低原子価チタンの発生法を開発し,新規なdual-modeカップリング重合法およびアルキン[2+2+2]環化付加反応の新触媒系を開発したことは,高分子合成化学および有機合成・触媒化学の分野に起用できる成果で有ると考えられる。

Report

(4 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report
  • 2017 Research-status Report
  • Research Products

    (13 results)

All 2020 2019 2018 2017

All Journal Article (3 results) (of which Peer Reviewed: 3 results) Presentation (10 results)

  • [Journal Article] Synthesis and vitamin D receptor affinity of 16-oxa vitamin D3 analogues2019

    • Author(s)
      Kouta Ibe, Takeshi Yamada and Sentaro Okamoto
    • Journal Title

      Organic and Bioorganic Chemistry

      Volume: 17 Issue: 48 Pages: 10188-10200

    • DOI

      10.1039/c9ob02339a

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Alkyne [2 + 2 + 2] Cyclotrimerization Catalyzed by a Low-Valent Titanium Reagent Derived from CpTiX3 (X = Cl, O-i-Pr), Me3SiCl, and Mg or Zn2018

    • Author(s)
      Sentaro Okamoto, Takeshi Yamada, Yu-ki Tanabe, and Masaki Sakai
    • Journal Title

      Organometallics

      Volume: 37 Issue: 23 Pages: 4431-4438

    • DOI

      10.1021/acs.organomet.8b00678

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Silica-Supported Silver as a Green and Sustainable Catalyst for the [3+2]-Cycloaddition Reaction of Azomethine Ylides with 2'-Hydroxychalcone Derivatives2018

    • Author(s)
      Suchithra Madhavan, Sentaro Okamoto
    • Journal Title

      ChemCatChem

      Volume: 10 Issue: 9 Pages: 2014-2018

    • DOI

      10.1002/cctc.201702035

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Presentation] Development of dual-mode coupling polymerization by a low-valent titanium reagent Ti(O-i-Pr)4/Me3SiCl/Mg2020

    • Author(s)
      Yuya Kimura, Nana Kikuta, Yousuke Tasuda, Takaya Uchida, Takeshi Yamada, Sentaro Okamoto
    • Organizer
      第100回日本化学会春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Synthesis and Vitamin D Receptor Affinity of 16-Oxa Vitamin D3 Derivatives.-12020

    • Author(s)
      Mayu Ogami, Kouta Ibe, Takeshi Yamada, Sentaro Okamoto
    • Organizer
      第100回日本化学会春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Synthesis and Vitamin D Receptor Affinity of 16-Oxa Vitamin D3 Derivatives.-22020

    • Author(s)
      Kouta Ibe, Mayu Ogami, Takeshi Yamada, Sentaro Okamoto
    • Organizer
      第100回日本化学会春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 低原子価チタン反応剤によるdual-modeカップリング重合法の開発2019

    • Author(s)
      木村祐也,菊田奈菜,安田葉助,山田健,岡本専太郎
    • Organizer
      第9回CSJフェスタ
    • Related Report
      2019 Annual Research Report
  • [Presentation] CoCl2-6H2O/dipimp/Zn触媒によるアルキンの[2+2+2]環化付加反応を用いた多分岐高分子の合成2019

    • Author(s)
      菊田 奈菜,山田 健,岡本 専太郎
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] インドール酪酸(IBA)の生物活性の解明を目指したオーキシンアナログの合成2019

    • Author(s)
      山本春佳・島田美咲・山田健・中川理絵・岡本専太郎
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] 二価チタン反応剤によるアルキンの分子内ビニル-およびアレニル-チタン化環化反応2018

    • Author(s)
      中田春樹,竹村真太朗,太田登茂樹,山田健,岡本専太郎
    • Organizer
      第8回CSJ化学フェスタ
    • Related Report
      2018 Research-status Report
  • [Presentation] Co触媒によるアルキン環化付加重合を用いた多分岐高分子の合成2018

    • Author(s)
      菊田奈菜,進藤卓宏,岡本専太郎
    • Organizer
      第8回CSJ化学フェスタ
    • Related Report
      2018 Research-status Report
  • [Presentation] 低原子価チタンを鍵反応としたent-Artmeisininの合成研究2018

    • Author(s)
      佐野俊市郎,岡本専太郎,山田健
    • Organizer
      第8回CSJ化学フェスタ
    • Related Report
      2018 Research-status Report
  • [Presentation] アルキン[2+2+2]環化付加反応による分岐高分子の合成2017

    • Author(s)
      1) 進藤卓宏,菊田奈々,岡本専太郎
    • Organizer
      第7回CSJ化学フェスタ
    • Related Report
      2017 Research-status Report

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Published: 2017-04-28   Modified: 2021-02-19  

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