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Synthesis of Optically Active Polymers Having Axially Chiral Allenic Units in Their Main Chains

Research Project

Project/Area Number 16K13989
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeMulti-year Fund
Research Field Synthetic chemistry
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)

Co-Investigator(Renkei-kenkyūsha) NAKANO TAMAKI  北海道大学, 触媒科学研究所, 教授 (40227856)
Project Period (FY) 2016-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
Fiscal Year 2017: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2016: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Keywordsアレン / パラジウム / 軸不斉 / 求核置換反応 / 均一系触媒 / 不斉合成 / ホスフィン / 配位子 / 求核剤 / 光学活性ポリマー / 不斉重合
Outline of Final Research Achievements

Palladium-catalyzed reaction between a bifunctional electrophile (3-bromo-2,4-pentadienyl ester) and a bifunctional nucleophile (bis-malonate) provided polymers/oligomers having axially chiral allenic units in their main chains. Using a chiral palladium catalyst, optically active polymers/oligomers based on the axially chiral allenic moieties were obtained. The optically active polymers obtained from a bifunctional nucleophile having a siloxane junction could be converted to the corresponding monomeric allene quantitatively by the hydrofluoric acid treatment. The monomeric allene thus obtained was analyzed by the chiral HPLC to determine the stereoselectivity of the asymmetric polymerization process.

Report

(3 results)
  • 2017 Annual Research Report   Final Research Report ( PDF )
  • 2016 Research-status Report
  • Research Products

    (24 results)

All 2018 2017 2016

All Journal Article (9 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 9 results,  Open Access: 2 results,  Acknowledgement Compliant: 2 results) Presentation (15 results) (of which Int'l Joint Research: 6 results,  Invited: 9 results)

  • [Journal Article] Molybdenum-Catalyzed Enantioselective Synthesis of Planar-Chiral (5h-Phosphacyclopentadienyl)manganese(I) Complexes and Application in Asymmetric Catalysis2017

    • Author(s)
      Ogasawara, M.; Tseng, Y.-Y.; Uryu, M.; Ohya, N.; Chang, N.; Ishimoto, H.; Arae, S.; Takahashi, T.; Kamikawa, K.
    • Journal Title

      Organometallics

      Volume: 36 Issue: 20 Pages: 4061-4069

    • DOI

      10.1021/acs.organomet.7b00704

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Atropisomeric chiral diiododienes, (Z,Z)-2,3-di(1-iodoalkylidene)tetralins: Synthesis, enantiomeric resolution, and application in asymmetric catalysis2017

    • Author(s)
      M. Ogasawara, H. Sasa, H. Hu, Y. Amano, H. Nakajima, N. Takenaga, K. Nakajima, Y. Kita, T. Takahashi, T. Dohi
    • Journal Title

      Org. Lett.

      Volume: 19 Issue: 15 Pages: 4102-4105

    • DOI

      10.1021/acs.orglett.7b01876

    • NAID

      120006556293

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Palladium-Catalyzed SN2'-Cyclization of Ambivalent (Bromoalkadienyl)malonates: Preparation of Medium- to Large-Membered Endocyclic Allenes2017

    • Author(s)
      Ichio, H.; Murakami, H.; Chen, Y.-C.; Takahashi, T.; Ogasawara, M.
    • Journal Title

      J. Org. Chem.

      Volume: 82 Issue: 14 Pages: 7503-7511

    • DOI

      10.1021/acs.joc.7b01204

    • NAID

      120006556298

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Isolation and phototransformation of enantiomerically pure iridium(iii) bis[(4,6-difluorophenyl)pyridinato-N,C2]picolinate2017

    • Author(s)
      Wang Yue、Harada Takunori、Shiota Yoshihito、Yoshizawa Kazunari、Wang Heng、Wang Sheng、Ye Xichong、Ogasawara Masamichi、Nakano Tamaki
    • Journal Title

      RSC AdV

      Volume: 7 Issue: 47 Pages: 29550-29553

    • DOI

      10.1039/c7ra04141a

    • NAID

      120007141569

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Enantioselective Synthesis of Planar-Chiral Transition-Metal Complexes by Homogeneous Olefi n-Metathesis Reactions and Their Application in Asymmetric Catalysis2017

    • Author(s)
      小笠原正道
    • Journal Title

      Bulletin of Japan Society of Coordination Chemistry

      Volume: 70 Issue: 0 Pages: 14-21

    • DOI

      10.4019/bjscc.70.14

    • NAID

      130006329808

    • ISSN
      1882-6954, 1883-1737
    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] モリブデン触媒不斉オレフィン・メタセシスによる面不斉遷移金属錯体の触媒的不斉合成2017

    • Author(s)
      小笠原正道
    • Journal Title

      Organometallic News

      Volume: 1 Pages: 52-57

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Concise Asymmetric Construction of C2-Symmetric 1,9-Diarylnonanoids Using Hypervalent Silicon Complex: Total Synthesis of (-)-Ericanone2016

    • Author(s)
      Kotani, S.; Kai, K.; Shimoda, Y.; Hu, H.; Gao, S.; Sugiura, M.; Ogasawara, M.; Nakajima, M.
    • Journal Title

      Chem. Asian J.

      Volume: 11 Issue: 3 Pages: 376-379

    • DOI

      10.1002/asia.201501080

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Bithiophene with Winding Vine-Shaped Molecular Asymmetry: Preparation, Structural Characterization, and Enantioselective Synthesis2016

    • Author(s)
      Toyomori, Y.; Tsuji, S.; Mitsuda, S.; Okayama, Y.; Mori, A.; Kobayashi, T.; Miyazaki, Y.; Yaita, T.; Arae, S.; Takahashi, T.; Ogasawara, M.
    • Journal Title

      Bull. Chem. Soc. Jpn.

      Volume: 89 Issue: 12 Pages: 1480-1486

    • DOI

      10.1246/bcsj.20160265

    • NAID

      130005316221

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Cross-Coupling Reactions Other Than Suzuki-Miyaura Coupling2016

    • Author(s)
      Ogasawara, M.
    • Journal Title

      Science of Synthesis, Reference Library 2016/5a (N-Heterocyclic Carbenes in Catalytic Organic Synthesis 1)

      Volume: - Pages: 141-159

    • DOI

      10.1055/sos-sd-223-00051

    • ISBN
      9783132012813, 9783132407633
    • Related Report
      2016 Research-status Report
    • Peer Reviewed
  • [Presentation] 面不斉フェロセンを基盤とするP-オレフィン配位子の開発と応用2018

    • Author(s)
      瓜生 瑞穂、中島 清彦、小笠原 正道
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Palladium-Catalyzed Synthesis of Allenic Oligomers/Polymers2018

    • Author(s)
      Yen-Chou Chen, Yue Wang, Tamaki Nakano and Masamichi Ogasawara
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Atropisomeric Chiral Dienes in Asymmetric Catalysis2018

    • Author(s)
      Masamichi Ogasawara
    • Organizer
      International Congress on Pure & Applied Chemistry 2017
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis and Catalytic Applications of Novel Atropisomeric Chiral Dienes2018

    • Author(s)
      Masamichi Ogasawara
    • Organizer
      Pure and Applied Chemistry International Conference 2018
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 3-ブロモ-2,4-ペンタジエニル・エステル類を基質とするパラジウム触媒二重求核置換反応によるC2-対称軸不斉アレンの触媒的不斉合成2017

    • Author(s)
      陳 彦洲、小笠原 正道
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾大学・日吉キャンパス(神奈川県横浜市)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] Total Synthesis of Axially Chiral Naturally Occurring Allenes Utilizing Palladium-Catalyzed Allene Synthesis Reaction2017

    • Author(s)
      Ogasawara, M.
    • Organizer
      Pure and Applied Chemistry International Conference 2017 (PACCON 2017)
    • Place of Presentation
      Bangkok, Thailand
    • Year and Date
      2017-02-02
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Palladium-Catalyzed Synthesis of Allenes by Double Nucleophilic Substitution on 3-Bromopenta-2,4-dienyl Esters2017

    • Author(s)
      Yen-Chou Chen, Masamichi Ogasawara
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Synthesis and Application of Novel Chiral Phosphine Ligands Having Diferrocenylphosphino-Donor Moieties2017

    • Author(s)
      Masamichi Ogasawara, Hao Hu, Hiroki Ichiryu, Naoki Seki, and Kiyohiko Nakajima
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Enantioselective Synthesis of Metallocene-Fused Planar-Chiral 4-Pyridones and 4-Dialkylaminopyridines and Their Application in Asymmetric Catalysis2017

    • Author(s)
      Qiang Liu, Shiro Wada, Ryosuke Kimura, Risa Yasue, Kazuhiro Yoshida and Masamichi Ogasawara
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 均一系遷移金属触媒による遷移金属錯体の不斉合成法の開発と応用2017

    • Author(s)
      小笠原 正道
    • Organizer
      2017年日本化学会中国四国支部徳島地区化学講演会
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] 均一系遷移金属触媒による立体選択的分子変換反応2017

    • Author(s)
      小笠原 正道
    • Organizer
      第11回触媒道場
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] Atropisomeric Chiral Dienes in Asymmetric Catalysis2017

    • Author(s)
      Masamichi Ogasawara
    • Organizer
      2017 International Symposium on Chemistry Frontiers
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 均一系遷移金属触媒による遷移金属錯体の不斉合成2017

    • Author(s)
      小笠原 正道
    • Organizer
      第33回若手化学者のための化学道場
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] Mo-Catalyzed Asymmetric Synthesis of P-Stereogenic Phosphine Derivatives by "Formal" Cross-Metathesis on Arene-Cr Complexes2017

    • Author(s)
      Masamichi Ogasawara
    • Organizer
      International Symposium on Pure & Applied Chemistry 2017
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Design and Synthesis of Phosphine-Olefin Ligands with Planar-Chiral Metal Complex Scaffold and Application in Asymmetric Catalysis2017

    • Author(s)
      Masamichi Ogasawara
    • Organizer
      The 253rd ACS National Meeting
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited

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Published: 2016-04-21   Modified: 2019-03-29  

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