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Asymmetric Synthesis of Novel Chiral Silicon-Containing pi-Conjugated System and Investigation of the Function

Research Project

Project/Area Number 25810060
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Synthetic chemistry
Research InstitutionNagoya University

Principal Investigator

YUKI Naganawa  名古屋大学, 工学(系)研究科(研究院), 助教 (00613233)

Project Period (FY) 2013-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000)
Fiscal Year 2014: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2013: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
Keywords有機合成 / 不斉反応 / 遷移金属 / ロジウム / イリジウム / ケイ素 / 触媒 / 触媒的不斉合成 / フェナントロリン / 還元
Outline of Final Research Achievements

Recently, catalytic asymmetric constructions of chiral silicon centers have been of great interest considering their unique chemical and physical properties. In this context, we demonstrated Rh-catalyzed enantioselective desymmetrizing intramolecular hydrosilylation of symmetrically disubstituted hydrosilanes. The original axially chiral phenanthroline ligand was found to work as an effective chiral catalyst for this transformation. A chiral silicon-stereogenic center is one of the chiral motifs gaining much attention in asymmetric syntheses and the present protocol provides cyclic five-membered organosilanes with a chiral silicon center with high enantioselectivity. Next, we are interested in application of Ir-catalyzed direct C-H silylation to the construction of chiral silicon center. Also for this transformation, the chiral phenanthrolines worked as effective ligands to give the desired products with moderate enantioselectivity.

Report

(3 results)
  • 2014 Annual Research Report   Final Research Report ( PDF )
  • 2013 Research-status Report
  • Research Products

    (11 results)

All 2015 2014 2013

All Journal Article (1 results) (of which Peer Reviewed: 1 results,  Acknowledgement Compliant: 1 results) Presentation (10 results)

  • [Journal Article] Design of novel chiral N,N,O-tridentate phenanthroline ligands and its application to enantioselective addition of organozinc reagents to aldehydes2014

    • Author(s)
      Naganawa, Y.; Namba, T.; Aoyama, T.; Shoji, K.; Nishiyama, H.
    • Journal Title

      Chem. Commun.

      Volume: 50 Issue: 87 Pages: 13224-13227

    • DOI

      10.1039/c4cc05020g

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] ロジウムおよびイリジウム触媒を用いるヒドロシランの不斉非対称化反応の開発2015

    • Author(s)
      難波知也, 川岸真友, 永縄友規, 西山久雄
    • Organizer
      日本化学会 第95春季年会
    • Place of Presentation
      日本大学船橋キャンパス
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] ロジウム触媒による分子内不斉ヒドロシリル化を経由するキラルケイ素中心構築法の開発2014

    • Author(s)
      川岸真友, 永縄友規, 西山久雄
    • Organizer
      第45回 中部化学関係学協会支部連合秋季大会
    • Place of Presentation
      中部大学春日井キャンパス
    • Year and Date
      2014-11-29 – 2014-11-30
    • Related Report
      2014 Annual Research Report
  • [Presentation] キラルフェナントロリン配位子BinThro を触媒に用いた非対称化によるキラルケイ素中心構築法の開発2014

    • Author(s)
      難波知也, 川岸真友, 永縄友規, 西山久雄
    • Organizer
      第 61 回 有機金属化学討論会
    • Place of Presentation
      九州大学病院キャンパス
    • Year and Date
      2014-09-23 – 2014-09-25
    • Related Report
      2014 Annual Research Report
  • [Presentation] Design of BINOL-Derived Axially Chiral Phenanthroline Ligands Being Applicable to a Wide Range of Metal Catalysts2014

    • Author(s)
      Yuki Naganawa, Hisao Nishiyama
    • Organizer
      ICOMC 2014
    • Place of Presentation
      Royton Sapporo
    • Year and Date
      2014-07-13 – 2014-07-18
    • Related Report
      2014 Annual Research Report
  • [Presentation] Syntheses of Chiral Silicon Center via Enantioselective Desymmetrization atalyzed by Rh and Ir Chiral Phenanthroline Catalysts2014

    • Author(s)
      Tomoya Namba, Mayu Kawagishi, Yuki Naganawa, Hisao Nishiyama
    • Organizer
      IGER International Symposium on Chemical Science in Asia
    • Place of Presentation
      Nagoya University
    • Year and Date
      2014-05-26 – 2014-05-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] イリジウム触媒による分子内不斉直截的CーHシリル化を経由するキラルケイ素中心構築法の開発2014

    • Author(s)
      難波知也・永縄友規・西山久雄
    • Organizer
      第94日本化学会春季年会
    • Place of Presentation
      名古屋大学
    • Related Report
      2013 Research-status Report
  • [Presentation] ロジウム触媒による分子内不斉ヒドロシリル化を経由するキラルケイ素中心構築法の開発2014

    • Author(s)
      川岸真友・難波知也・永縄友規・西山久雄
    • Organizer
      第94日本化学会春季年会
    • Place of Presentation
      名古屋大学
    • Related Report
      2013 Research-status Report
  • [Presentation] 四置換光学活性ケイ素中心の構築を目指す脱対称ヒドロシリル化反応の開発2013

    • Author(s)
      難波知也.近藤真美.永縄友規.西山久雄
    • Organizer
      第46回 有機金属若手の会 夏の学校
    • Place of Presentation
      宮城蔵王ロイヤルホテル
    • Related Report
      2013 Research-status Report
  • [Presentation] 新規キラルフェナントロリン配位子の設計と不斉ケイ素中心構築手法への応用2013

    • Author(s)
      永縄友規,難波知也,近藤真美,西山久雄
    • Organizer
      第60回 有機金属化学討論会
    • Place of Presentation
      学習院大学
    • Related Report
      2013 Research-status Report
  • [Presentation] 新規キラルフェナントロリン配位子の設計と不斉ケイ素中心構築手法への応用2013

    • Author(s)
      難波知也,近藤真美,川岸真友,永縄友規,西山久雄
    • Organizer
      第3回 CSJ化学フェスタ
    • Place of Presentation
      タワーホール船堀
    • Related Report
      2013 Research-status Report

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Published: 2014-07-25   Modified: 2019-07-29  

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