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Controlled organic synthesis utilizing propylene polymerization catalysts

Research Project

Project/Area Number 15H03807
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionThe University of Tokyo

Principal Investigator

Nozaki kyoko  東京大学, 大学院工学系研究科(工学部), 教授 (60222197)

Project Period (FY) 2015-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥17,680,000 (Direct Cost: ¥13,600,000、Indirect Cost: ¥4,080,000)
Fiscal Year 2017: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2016: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2015: ¥13,520,000 (Direct Cost: ¥10,400,000、Indirect Cost: ¥3,120,000)
Keywords有機化学 / プロピレン / オリゴマー化
Outline of Final Research Achievements

By using metallocene catalysts, oligomers of propylene were obtained starting from dialkyl zinc as an initiator with extremely high stereospecificity. More importantly, after oxidation of the oligomerization products, the mixture of alcohols with different chain-lengths were successfully purified by reverse-phase high-performance liquid chromatography.
Both all syn- and all anti- structures were obtained employing C2-symmetric and Cs-symmetric catalysts, respectively, as was reported for the propylene polymerization. In case for the C2-symmetric complex, optical resolution of the chiral complex allowed the asymmetric synthesis and thus a single enantiomer was obtained in over 99% ee.

Academic Significance and Societal Importance of the Research Achievements

単離したall-synオリゴマーは灰色ガンの油脂の主要成分である(2R、4R、6R、8R)-2,4,6,8-テトラメチルデカン酸合成に、all-antiオリゴマーは昆虫Antitrogus parvulusラのホルモンの合成中間体である、rel-(2R,4S,6R,8S)-2,4,6,8‐テトラメチルウンデカン‐1‐オール合成に用いることができた。これらの化合物の生合成経路がプロピオニルCoAによって媒介されるクライゼン縮合であることを考慮すると、本合成はビルディングブロックとして同じC 3単位を使用しており、同時に得られる他のオリゴマーは生物学的活性を発現し得る。

Report

(4 results)
  • 2018 Final Research Report ( PDF )
  • 2017 Annual Research Report
  • 2016 Annual Research Report
  • 2015 Annual Research Report
  • Research Products

    (15 results)

All 2018 2017 2016 Other

All Journal Article (2 results) (of which Peer Reviewed: 2 results,  Acknowledgement Compliant: 1 results) Presentation (10 results) (of which Int'l Joint Research: 2 results) Remarks (3 results)

  • [Journal Article] Single-Step Construction of the anti-Deoxypropionate Motif from Propylene: Formal Total Synthesis of the Cuticular Hydrocarbons Isolated from Antitrogus parvulus2018

    • Author(s)
      Murayama Toshiki、Nozaki Kyoko
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 57 Issue: 35 Pages: 11394-11398

    • DOI

      10.1002/anie.201804711

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] One-step catalytic asymmetric synthesis of all-/syn/deoxypropionate motif from propylene: Total synthesis of (-)tetramethyldecanoic acid2016

    • Author(s)
      Yusuke Ota, Toshiki Murayama, Kyoko Nozaki
    • Journal Title

      Proc. Nat. Acad. Sci. USA

      Volume: 113 Issue: 11 Pages: 2857-2857

    • DOI

      10.1073/pnas.1518898113

    • Related Report
      2016 Annual Research Report 2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Single-Step Construction of Deoxypropionate Motif by Stereospecific Propylene Oligomerization.2018

    • Author(s)
      Toshiki Murayama, Yusuke Ota, Kyoko Nozaki
    • Organizer
      The Ninth International Forum on Chemistry of Functional Organic Chemicals (IFOC-9)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Development of stereospecific propylene oligomerization toward single-step synthesis of deoxypropionate motif.2018

    • Author(s)
      Toshiki Murayama, Yusuke Ota, Kyoko Nozaki
    • Organizer
      28th International Conference on Organometallic Chemistry (ICOMC 2018)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Single-step synthesis of deoxypropionate motif in natural products by2017

    • Author(s)
      村山 駿輝・太田 祐介・野崎 京子
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] プロピレンのイソおよびシンジオ特異的オリゴマー化によるデオキシプロピオナート構造の構築2017

    • Author(s)
      村山 駿輝・太田 祐介・野崎 京子
    • Organizer
      第7回CSJ化学フェスタ2017
    • Related Report
      2017 Annual Research Report
  • [Presentation] プロピレンのイソおよびシンジオ特異的オリゴマー化によるデオキシプロピオナート構造の構築2017

    • Author(s)
      村山 駿輝・太田 祐介・野崎 京子
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] プロピレンの不斉オリゴマー化を利用したデオキシプロピオナート構造の構築と(-)-テトラメチルデカン酸の合成への応用2016

    • Author(s)
      村山 駿輝・太田 祐介・野崎 京子
    • Organizer
      第109回有機合成シンポジウム
    • Place of Presentation
      東京工業大学 東京都目黒区
    • Year and Date
      2016-06-08
    • Related Report
      2015 Annual Research Report
  • [Presentation] デオキシプロピオナート構造の1段階構築による(2R,4R,6R,8R)-2,4,6,8-テトラメチルデカン酸の合成2016

    • Author(s)
      村山 駿輝・太田 祐介・野崎 京子
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      東京工業大学 東京都目黒区
    • Year and Date
      2016-03-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] 7.デオキシプロピオナート構造の構築に向けたプロピレンの不斉オリゴマー化2016

    • Author(s)
      村山 駿輝・太田 祐介・野崎 京子
    • Organizer
      第63回有機金属化学討論会
    • Related Report
      2016 Annual Research Report
  • [Presentation] 16.One-Step Catalytic Construction of Deoxypropionate Motif by Propylene Oligomerization.2016

    • Author(s)
      Murayama, T., Ota, Y., Nozaki, K.
    • Organizer
      20th International Symposium on Homogeneous Catalysis (ISHCXX)
    • Related Report
      2016 Annual Research Report
  • [Presentation] 24.プロピレンの不斉オリゴマー化を利用したデオキシプロピオナート構造の構築と(-)-テトラメチルデカン酸の合成への応用2016

    • Author(s)
      村山 駿輝・太田 祐介・野崎 京子
    • Organizer
      第109回有機合成シンポジウム
    • Related Report
      2016 Annual Research Report
  • [Remarks] 野崎研究室HP

    • URL

      http://park.itc.u-tokyo.ac.jp/nozakilab/

    • Related Report
      2017 Annual Research Report
  • [Remarks]

    • URL

      http://park.itc.u-tokyo.ac.jp/nozakilab/publication/index.html

    • Related Report
      2016 Annual Research Report
  • [Remarks] 東京大学大学院工学系研究科化学生命工学専攻野崎研究室

    • URL

      http://park.itc.u-tokyo.ac.jp/nozakilab/

    • Related Report
      2015 Annual Research Report

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Published: 2015-04-16   Modified: 2020-03-30  

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