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Enantioselective Synthesis and Application of Functional Planar-Chiral Transition-Metal Complexes

Research Project

Project/Area Number 18H01979
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 33020:Synthetic organic chemistry-related
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) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥17,420,000 (Direct Cost: ¥13,400,000、Indirect Cost: ¥4,020,000)
Fiscal Year 2020: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2019: ¥5,460,000 (Direct Cost: ¥4,200,000、Indirect Cost: ¥1,260,000)
Fiscal Year 2018: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Keywords面不斉 / 遷移金属錯体 / 不斉合成 / 均一系触媒 / メタロセン / オレフィン・メタセシス / 速度論分割 / 非対称化 / ホスファフェロセン / メタセシス / オレフィン / 測度論分割 / モリブデン / パラジウム / エナンチオ選択性 / フェロセン / 不斉配位子 / エナンチオ選択的 / キラルカラム / 多糖類 / 異性体分離
Outline of Final Research Achievements

The purposes of this research project is development of novel enantioselective synthetic methods of various chiral transition-metal complexes utilizing well-developed stereoselective organic transformations. The target tansition-metal complexes in this study are potential chiral catalysts, chiral ligands, and chiral reagents. And thus, application of the products from the developed asymmetric transformations in the subsequent "second" asymmetric reactions as chiral catalysts/chiral ligands/chiral reagents was also examined. The three topics examind through this research projects are: (1) synthesis and applications of phosphine-olefin ligands having planar-chiral ferrocene scaffold, (2) enantioselective synthesis of planar-chiral ferrocene-fused cyclic phosphonic acids, (3) development of diastereo- and enantioselective metathesis dimerization/kinetic resolution of racemic planar-chiral vinylferrocenes.

Academic Significance and Societal Importance of the Research Achievements

「立体選択的合成手法の開発」は有機合成化学における最重要課題の一つであり、多くの研究がなされている。一方、遷移金属原子を含む化合物では通常の有機化合物ではあり得ない多様な三次元構造が形成される。遷移金属錯体の複雑な立体化学を制御する試みは、ごく最近まで報告例は皆無であった。近年、キラルな遷移金属化合物が有機合成において有用であることが示されており、光学活性キラル遷移金属錯体を効率的に合成する手法の開発はこの分野の今後の発展のための急務である。本研究では、この問題への一つの解決を示すものである。

Report

(4 results)
  • 2021 Final Research Report ( PDF )
  • 2020 Annual Research Report
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • Research Products

    (40 results)

All 2021 2020 2019 2018

All Journal Article (11 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 11 results,  Open Access: 4 results) Presentation (29 results) (of which Int'l Joint Research: 8 results,  Invited: 4 results)

  • [Journal Article] Estimating Effective Steric and Electronic Impacts of a Ferrocenyl Group in Organophosphines2021

    • Author(s)
      Hu Hao、Ichiryu Hiroki、Nakajima Kiyohiko、Ogasawara Masamichi
    • Journal Title

      ACS Omega

      Volume: 6 Issue: 8 Pages: 5981-5989

    • DOI

      10.1021/acsomega.1c00307

    • NAID

      120007146096

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] C1-Symmetric Binap Derivative Featuring Single Diferrocenylphosphino-Donor Moiety2021

    • Author(s)
      Enomoto Yuuki、Ichiryu Hiroki、Hu Hao、Ura Yasuyuki、Ogasawara Masamichi
    • Journal Title

      Organometallics

      Volume: 40 Issue: 8 Pages: 1020-1024

    • DOI

      10.1021/acs.organomet.1c00132

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Stereodivergent Access to Trisubstituted Alkenylboronate Esters through Alkene Isomerization2021

    • Author(s)
      Segura Lucas、Massad Itai、Ogasawara Masamichi、Marek Ilan
    • Journal Title

      Organic Letters

      Volume: 23 Issue: 23 Pages: 9194-9198

    • DOI

      10.1021/acs.orglett.1c03513

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [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] Oxidative Cyclization ofo-(1-Hydroxy-2-alkynyl)-N-tosylanilides for the Synthesis of 4-Quinolones2020

    • Author(s)
      Ueda Jun-ichi、Enomoto Yuuki、Seki Mizuki、Konishi Takuma、Ogasawara Masamichi、Yoshida Kazuhiro
    • Journal Title

      The Journal of Organic Chemistry

      Volume: 85 Issue: 10 Pages: 6420-6428

    • DOI

      10.1021/acs.joc.0c00245

    • 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] 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] 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 Annual Research 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 Annual Research 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 Annual Research Report
    • Peer Reviewed
  • [Presentation] 面不斉ビニルフェロセン類の立体選択的メタセシス不斉二量化反応2021

    • Author(s)
      田上 遥、西本 昂司、大路 健仁、大木 靖弘、小笠原 正道
    • Organizer
      第67回有機金属化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 単一のジフェロセニルホスフィノ基を有するC1対称Binap誘導体の合成と応用2021

    • Author(s)
      榎本 裕貴、一柳 浩輝、胡 ハオ、浦 康之、小笠原 正道
    • Organizer
      第67回有機金属化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 有機ホスフィン類におけるフェロセニル基の立体的/電子的影響の定量化2021

    • Author(s)
      胡 ハオ、一柳 浩輝、中島 清彦、小笠原 正道
    • Organizer
      第67回有機金属化学討論会
    • Related Report
      2020 Annual Research Report
  • [Presentation] 面不斉フェロセン縮環ホスホン酸のエナンチオ選択的合成法の開発と応用2021

    • Author(s)
      大路 健仁、岡崎 願之晋、劉 強、安江 里紗、吉田 和弘、小笠原 正道
    • Organizer
      2021年日本化学会中国四国支部大会
    • Related Report
      2020 Annual Research Report
  • [Presentation] パラジウム触媒による主鎖に軸不斉アレン構造を有する光学活性ポリマーの合成2020

    • Author(s)
      小笠原 正道
    • Organizer
      第69回高分子討論会
    • Related Report
      2020 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] 多糖類を固定相に有するキラルHPLCカラムによる非鏡像関係にある異性体の分離2019

    • Author(s)
      榎本 裕貴、大路 健仁、瓜生 瑞穂、ヤン シーチェン、片岡 綾美、大西 敦、小笠原 正道
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2019 Annual Research Report
  • [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
      第66回有機金属化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] ビス(2ーブロモ1,3-ジエン)をモノマーとするパラジウム触媒による軸不斉アレン・ポリマーの合成2019

    • Author(s)
      陳 彦洲、岩本 啓汰、宋 志毅、中野 環、小笠原 正道
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Palladium-Catalyzed Synthesis of Optically Active Axially Chiral Allenic Polymers2019

    • Author(s)
      Ogasawara, M.
    • Organizer
      The 14th International Conference on Cutting-Edge Organic Chemistry in Asia (ICCEOCA-14)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 多糖類ベースのキラルHPLCカラムによる非エナンチオマー異性体混合物の分離2019

    • Author(s)
      大路 健仁、榎本 裕貴、大西 敦、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] ω-位に求核部位を有する3-ブロモ-1,3-アルカジエン類のパラジウム触媒環化反応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
      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] ジシロキサン架橋ビス(2-ブロモ-1,3-ジエン)のパラジウム触媒反応による軸不斉アレン・ポリマーの合成2019

    • Author(s)
      岩本 啓汰、陳 彦洲、宋 志毅、中野 環、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] 嵩高い置換基を有する新規Segphos誘導体の合成と遷移金属触媒不斉反応への応用2019

    • Author(s)
      谷 有香里、澤野 恵理、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] alladium-Catalyzed Synthesis of Optically Active Axially Chiral Allenic Polymers2019

    • Author(s)
      Ogasawara, M.
    • Organizer
      The 18th Asian Chemical Congress (ACC2019)
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [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
      2018 Annual Research Report
  • [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 Annual Research Report
  • [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
      2018 Annual Research 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
    • Related Report
      2018 Annual Research 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
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Pd-Catalyzed Synthesis of Axially Chiral Allenic Polymers2019

    • Author(s)
      Ogasawara, M.; Chen, Y.-C.; Wang, Y.; Nakano, T.
    • Organizer
      The Fifth International Forum on Advanced Technologies
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [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
      2018 Annual Research Report
  • [Presentation] パラジウム触媒による主鎖に軸不斉アレン構造を有するポリマーの合成2018

    • Author(s)
      陳 彦洲、王 ヤン、中野 環、小笠原 正道
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] フェロセン縮環した面不斉環状ホスホン酸類の不斉合成2018

    • Author(s)
      劉 強、安江 里紗、岡崎 願之晋、吉田 和弘、小笠原 正道
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 面不斉フェロセンを基盤とするホスフィンーオレフィン配位子の開発と不斉触媒反応への応用2018

    • Author(s)
      瓜生 瑞穂、片岡 綾美、小笠原 正道
    • Organizer
      第65回有機金属化学討論会
    • Related Report
      2018 Annual Research Report

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Published: 2018-04-23   Modified: 2023-01-30  

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