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Preparation of cyclophanes driven by pi-coordination of arenes to a transition-metal center

Research Project

Project/Area Number 18K19080
Research Category

Grant-in-Aid for Challenging Research (Exploratory)

Allocation TypeMulti-year Fund
Review Section Medium-sized Section 33:Organic chemistry and related fields
Research InstitutionThe University of Tokushima

Principal Investigator

OGASAWARA Masamichi  徳島大学, 大学院社会産業理工学研究部(理工学域), 教授 (70301231)

Project Period (FY) 2018-06-29 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000)
Fiscal Year 2019: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Fiscal Year 2018: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Keywordsシクロファン / メタセシス / クロム / 鉄 / パイ配位 / ルテニウム / モリブデン / オレフィン・メタセシス / π配位 / 遷移金属
Outline of Final Research Achievements

In this research, a novel method of preparing cyclophanes was examined. Our idea was the use of transition-metals as templates to assemble two alkenylarenes by the pi-coordination to the metal. Subsequent olefin metathesis between the two ligating arene moieties and removal of the metal template might afford the corresponding cyclophane derivatives. During the course of our investigations, it was found that the bis(alkenylarene)chromium species was difficult to synthesize. Then, we turned our attention to the metathesis dimerization of (alkenylarene)chromium tricarbonyl species, which afforded the expected dimerized products in high yields in the presence of the Grubbs-II catalyst. The metathesis reaction of 1-butenyl-1'-vinylferrocene proceeded in the two different manners; one was the ring-closing metathesis giving the ferrocenophane, the other was the dimerization at the vinyl terminal, and the two reaction paths could be controlled by the proper choices of the conditions.

Academic Significance and Societal Importance of the Research Achievements

様々な機能を有する複雑な化合物を選択的に合成する手法は、有機合成における重要な技術である。なかでも、新たな「立体選択的合成手法」の開発は、活発な研究分野である。本研究では、「遷移金属触媒」を用いて「遷移金属化合物」を立体選択的に分子変換する新たな手法について検討した。遷移金属を含む化合物では、d軌道が結合に関与するため、古典的な有機化合物ではありえない特徴的な立体構造を示すものがある。本研究で対象としたのは、そのなかでも「面不斉」と呼ばれる立体現象の制御である。

Report

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

    (21 results)

All 2020 2019 2018

All Journal Article (7 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 7 results,  Open Access: 2 results) Presentation (14 results) (of which Int'l Joint Research: 7 results,  Invited: 3 results)

  • [Journal Article] Synthesis, Characterization, and Application of Segphos Derivative Having Diferrocenylphosphino-Donor Moieties2020

    • Author(s)
      Hao Hu, Hiroki Ichiryu, Naoki Seki, Kiyohiko Nakajima, Yasuhiro Ohki, Masamichi Ogasawara
    • Journal Title

      Organometallics

      Volume: 39 Issue: 6 Pages: 788-792

    • DOI

      10.1021/acs.organomet.9b00865

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Palladium-Catalyzed Three-Component Coupling of 1,1-Dibromoalkenes, Vinylzinc Chloride, and Soft Nucleophiles: One-Pot Synthesis of 1,3-Disubstituted Allenes2019

    • Author(s)
      Sawano Eri、Ogasawara Masamichi
    • Journal Title

      ACS Omega

      Volume: 4 Issue: 21 Pages: 19499-19504

    • DOI

      10.1021/acsomega.9b03444

    • NAID

      120006771283

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Versatile and Enantioselective Preparation of Planar-Chiral Metallocene-Fused 4-Dialkylaminopyridines and Their Application in Asymmetric Organocatalysis2019

    • Author(s)
      Yoshida Kazuhiro、Liu Qiang、Yasue Risa、Wada Shiro、Kimura Ryosuke、Konishi Takuma、Ogasawara Masamichi
    • Journal Title

      ACS Catalysis

      Volume: 10 Issue: 1 Pages: 292-301

    • DOI

      10.1021/acscatal.9b04438

    • NAID

      120006937693

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Palladium-Catalyzed Sequential Twofold Nucleophilic Substitution on 3-Bromopenta-2,4-dienyl Phosphate: Preparation of C1- and C2-Symmetric Doubly Functionalized Allenes2019

    • Author(s)
      Chen Yen-Chou、Ogasawara Masamichi
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 84 Issue: 19 Pages: 12463-12470

    • DOI

      10.1021/acs.joc.9b01933

    • NAID

      120006882793

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Theoretical Investigations of Rh-Catalyzed Asymmetric 1,4-Addition to Enones using Planar-Chiral Phosphine-Olefin Ligands2019

    • Author(s)
      Kawashima, K.; Sato, T.; Ogasawara, M.; Kamikawa, K.; Mori, S.
    • Journal Title

      J. Comput. Chem.

      Volume: 40 Issue: 1 Pages: 113-118

    • DOI

      10.1002/jcc.25550

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Application of Polysaccharide-Based Chiral HPLC Columns for Separation of Non-Enantiomeric Isomeric Mixtures of Organometallic Compounds2019

    • Author(s)
      Ogasawara, M.; Enomoto, Y.; Uryu, M.; Yang, X.; Kataoka, A.; Ohnishi, A.
    • Journal Title

      Organometallics

      Volume: 38 Issue: 2 Pages: 512-518

    • DOI

      10.1021/acs.organomet.8b00819

    • NAID

      120006556297

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Catalytic Enantioselective Aldol Reaction of Unprotected Carboxylic Acids under Phosphine Oxide Catalysis2018

    • Author(s)
      Kotani, S.; Yoshiwara, Y.; Ogasawara, M.; Sugiura, M.; Nakajima, M.
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 57 Issue: 48 Pages: 15877-15881

    • DOI

      10.1002/ange.201810599

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Presentation] キラルな遷移金属錯体の触媒的不斉合成2019

    • Author(s)
      小笠原 正道
    • Organizer
      理研セミナー
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] Enantioselective Synthesis of Planar-Chiral Ferrocene-Fused Cyclic Phosphonic Acids2019

    • Author(s)
      Okazaki, A.; Liu, Q.; Yasue, R.; Yoshida, K.; Ogasawara, M.
    • Organizer
      The Fifth International Forum on Advanced Technologies
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis and Application of C1-Symmetric Bisphosphine Ligand Having Diferrocenylphosphino-Donor Moiety2019

    • Author(s)
      Ichiryu, H.; Hu, H.; Ura, Y.; Ogasawara, M.
    • Organizer
      The Fifth International Forum on Advanced Technologies
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ジフェロセニルホスフィノ基を有する非対称不斉二座ホスフィン配位子の開発と応用2019

    • Author(s)
      一柳 浩輝、胡 淏、浦 康之、小笠原 正道
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2019 Annual Research Report 2018 Research-status Report
  • [Presentation] キラルな遷移金属錯体の触媒的不斉合成2019

    • Author(s)
      小笠原 正道
    • Organizer
      大阪大学大学院基礎工学研究科
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] RCM-Synthesis of Highly Enantioselective Phosphine-Olefin Ligands Based on Planar-Chiral Alkenylene-Bridged Transition-Metal Complexes2019

    • Author(s)
      Ogasawara, M.
    • Organizer
      The 23rd International Symposium on Olefin Metathesis and Related Chemistry (ISOM 23)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 面不斉フェロセンを基盤とする新規ホスフィン-オレフィン配位子の合成と応用2019

    • Author(s)
      榎本 裕貴、瓜生 瑞穂、浦 康之、小笠原 正道
    • Organizer
      2019年日本化学会中国四国支部大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] ビニルフェロセン類のホモメタセシスによる1,2-ジフェロセニルエチレン類の合成2019

    • Author(s)
      田上 遥、西本 昂司、小笠原 正道
    • Organizer
      2019年日本化学会中国四国支部大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 面不斉ビニルフェロセン類のホモメタセシス速度論分割2019

    • Author(s)
      西本 昂司、田上 遥、小笠原 正道
    • Organizer
      2019年日本化学会中国四国支部大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Catalytic Enantioselective Synthesis of Planar-Chiral Transition-Metal Complexes and Their Application in Organic Transformations2019

    • Author(s)
      Ogasawara, M.
    • Organizer
      Chiral India 2019: 8th International Conference & Exhibition
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 求核部位を有する2-ブロモ-1,3ジエン類のパラジウム触媒分子内環化における異常な選択性2019

    • Author(s)
      小西 卓磨、一尾 裕章、小笠原 正道
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Research-status Report
  • [Presentation] ynthesis and Application of C1-Symmetric Bisphosphine Ligand Having Diferrocenylphosphino-Donor Moiety2019

    • Author(s)
      Ichiryu, H.; Hu, H.; Ura, Y.; Ogasawara, M.
    • Organizer
      The Fifth International Forum on Advanced Technologies (IFAT 2019)
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Unusual Regioselectivity in Palladium-Catalyzed Cyclization of Nucleophile-Tethered 2-Bromo-1,3-dienes2019

    • Author(s)
      Konishi, T.; Ichio, H.; Ogasawara, M.
    • Organizer
      The Fifth International Forum on Advanced Technologies (IFAT 2019)
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Enantioselective Synthesis of Planar-Chiral Ferrocene-Fused Cyclic Phosphonic Acids2019

    • Author(s)
      Okazaki, A.; Liu, Q.; Yasue, R.; Yoshida, K.; Ogasawara, M.
    • Organizer
      The Fifth International Forum on Advanced Technologies (IFAT 2019)
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research

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Published: 2018-07-25   Modified: 2021-02-19  

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