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Multi-functional Rare Earth Catalysts for Precision Chemical Transformation

Research Project

Project/Area Number 17K05824
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Inorganic chemistry
Research InstitutionInstitute of Physical and Chemical Research

Principal Investigator

Nishiura Masayoshi  国立研究開発法人理化学研究所, 開拓研究本部, 専任研究員 (30332258)

Project Period (FY) 2017-04-01 – 2020-03-31
Project Status Completed (Fiscal Year 2019)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2019: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
Fiscal Year 2018: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Fiscal Year 2017: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywords希土類金属 / シクロペンタジエニル基 / C-H結合活性化 / 非極性オレフィンと極性オレフィンの共重合 / 自己修復材料 / 希土類アルキル錯体 / スカンジウム / 共重合 / 有機金属化学 / 高分子化学 / 不斉触媒 / 非極性と極性オレフィンとの共重合 / ポリオレフィン / 希土類触媒 / 有機合成 / 機能性ポリマー / 金属錯体化学 / 高分子合成 / 有機合成化学
Outline of Final Research Achievements

This project aimed to develop new catalysts, new reactions and new functional materials superior or complementary to the existing ones. By using half-sandwich rare-earth catalysts, we have achieved for the first time the copolymerization of ethylene and polar alpha-olefins in a controlled fashion, which afforded new functional polyolefins with excellent self-healing and shape-memory properties. We have synthesized a series of chiral half-sandwich rare-earth alkyl complexes that show excellent enantioselectivity and activity in various transformations such as asymmetric C-H alkylation via C=C insertion. This work has not only opened up new avenues in chemical science, but may also offer new entries into chemical industry innovation.

Academic Significance and Societal Importance of the Research Achievements

本研究の成果は、有機金属化学や触媒化学、有機合成化学、高分子合成化学などの基礎科学分野の新しいフロンティアの開拓のみならず、新たな知財の形成や新産業の創出にもつながることが期待できる。例えば、本研究を通して創製された新規自己修復ポリマーは、空気中だけでなく、水や酸、アルカリ性水溶液中でも優れた自己修復性能や形状記憶性能を示し、従来のものでは見られない実用性の高い新機能性材料として多方面から大きな期待が寄せられている。

Report

(4 results)
  • 2019 Annual Research Report   Final Research Report ( PDF )
  • 2018 Research-status Report
  • 2017 Research-status Report
  • Research Products

    (38 results)

All 2020 2019 2018 2017 Other

All Int'l Joint Research (3 results) Journal Article (18 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 18 results,  Open Access: 1 results) Presentation (10 results) (of which Int'l Joint Research: 3 results,  Invited: 2 results) Book (1 results) Remarks (4 results) Patent(Industrial Property Rights) (2 results) (of which Overseas: 1 results)

  • [Int'l Joint Research] Dalian University of Technology(中国)

    • Related Report
      2019 Annual Research Report
  • [Int'l Joint Research] Dalian University of Technology(中国)

    • Related Report
      2018 Research-status Report
  • [Int'l Joint Research] Dalian University of Technology(中国)

    • Related Report
      2017 Research-status Report
  • [Journal Article] Construction of All-Carbon Quaternary Stereocenters by Scandium-Catalyzed Intramolecular C-H Alkylation of Imidazoles with 1,1-Disubstituted Alkenes2020

    • Author(s)
      S. Lou, Z. Mo, M. Nishiura, Z. Hou
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 142 Pages: 1200-1205

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] CO2 Activation by Lewis Pairs Generated Under Copper Catalysis Enables Difunctionalization of Imines2020

    • Author(s)
      Z. Li, L. Zhang, M. Nishiura, G. Luo, Y. Luo, Z. Hou
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 142 Issue: 4 Pages: 1966-1974

    • DOI

      10.1021/jacs.9b11423

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Rare-Earth-Catalyzed C-H Silylation of Aromatic Heterocycles with Hydrosilanes2020

    • Author(s)
      W. Xu, H. Teng, Y. Luo, S. Lou, M. Nishiura, Z. Hou
    • Journal Title

      Chem Asian J.

      Volume: 15 Issue: 6 Pages: 753-756

    • DOI

      10.1002/asia.202000089

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Diastereodivergent [3+2] Annulation of Aromatic Aldimines with Alkenes via C-H Activation by Half-Sandwich Rare-Earth Catalysts2020

    • Author(s)
      X. Cong, G. Zhan, Z. Mo, M. Nishiura, Z. Hou
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 142 Issue: 12 Pages: 5531-5537

    • DOI

      10.1021/jacs.0c01171

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Co‐syndiospecific Alternating Copolymerization of Functionalized Propylenes and Styrene by Rare‐Earth Catalysts2020

    • Author(s)
      H. Wang, X. Wu, Y. Yang, M. Nishiura, Z. Hou
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 59 Issue: 18 Pages: 7173-7177

    • DOI

      10.1002/anie.201915760

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Scandium-Catalyzed Regio- and Stereoselective Cyclopolymerization of Functionalized α,ω-Dienes and Copolymerization with Ethylene2019

    • Author(s)
      H. Wang, Y. Zhao, M. Nishiura, Y. Yang, G. Luo, Y. Luo, Z. Hou
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 141 Issue: 32 Pages: 12624-12633

    • DOI

      10.1021/jacs.9b04275

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Synthesis of Self-Healing Polymers by Scandium-Catalyzed Copolymerization of Ethylene and Anisylpropylenes2019

    • Author(s)
      Haobing Wang, Yang Yang, Masayoshi Nishiura, Yuji Higaki, Atsushi Takahara, Zhaomin Hou
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Issue: 7 Pages: 3249-3257

    • DOI

      10.1021/jacs.8b13316

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Asymmetric C(sp)-H Addition of Terminal Alkynes to Cyclopropenes by a Chiral Gadolinium Catalyst2018

    • Author(s)
      Huailong Teng, Yuanhong Ma, Gu Zhan, Masayoshi Nishiura, Zhaomin Hou
    • Journal Title

      ACS Catalysis

      Volume: 8 Issue: 5 Pages: 4705-4709

    • DOI

      10.1021/acscatal.8b01189

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Metal-catalyzed C-H Activation for Polymer Synthesis and Functionalization2018

    • Author(s)
      Yang Yang, Masayoshi Nishiura, Haobing Wang, Zhaomin Hou
    • Journal Title

      Coordination Chemistry Reviews

      Volume: 376 Pages: 506-532

    • DOI

      10.1016/j.ccr.2018.08.017

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Ortho-Selective C-H Borylation of Aromatic Ethers with Pinacol-borane by Organo Rare-Earth Catalysts2018

    • Author(s)
      Can Xue, Yong Luo, Huailong Teng, Yuanhong Ma, Masayoshi Nishiura, Zhaomin Hou
    • Journal Title

      ACS Catalysis

      Volume: 8 Issue: 6 Pages: 5017-5022

    • DOI

      10.1021/acscatal.8b01364

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Yttrium-Catalyzed Regioselective alpha-C-H Silylation of Methyl Sulfides with Hydrosilanes2018

    • Author(s)
      Yong Luo, Huailong Teng, Can Xue, Masayoshi Nishiura, Zhaomin Hou
    • Journal Title

      ACS Catalysis

      Volume: 8 Issue: 9 Pages: 8027-8032

    • DOI

      10.1021/acscatal.8b02405

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Construction of Silicon-Stereogenic Silanes by Scandium-Catalyzed Intermolecular Alkene Hydrosilylation2018

    • Author(s)
      Gu Zhan, Huailong Teng, Yong Luo, Shao-Jie Lou, Masayoshi Nishiura, Zhaomin Hou
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 57 Issue: 38 Pages: 12342-12346

    • DOI

      10.1002/anie.201807493

    • Related Report
      2018 Research-status Report
    • Peer Reviewed
  • [Journal Article] B(C6F5)3/Amine-Catalyzed C(sp)-H Silylation of Terminal Alkynes with Hydrosilanes: Experimental and Theoretical Studies2018

    • Author(s)
      Yuanhong Ma, Shao-Jie Lou, Gen Luo, Yong Luo, Gu Zhan, Masayoshi Nishiura, Yi Luo, Zhaomin Hou
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 57 Issue: 46 Pages: 15222-15226

    • DOI

      10.1002/anie.201809533

    • Related Report
      2018 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Cationic Scandium Anisyl Species in Styrene Polymerization Using Anisole and N,N-Dimethyl-o-toluidine as Chain-Transfer Agents2017

    • Author(s)
      Yamamoto Atsushi、Nishiura Masayoshi、Yang Yang、Hou Zhaomin
    • Journal Title

      Organometallics

      Volume: 36 Issue: 23 Pages: 4635-4642

    • DOI

      10.1021/acs.organomet.7b00526

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Asymmetric Yttrium-Catalyzed C(sp3)-H Addition of 2-Methyl Azaarenes to Cyclopropenes2017

    • Author(s)
      Luo Yong、Teng Huai-Long、Nishiura Masayoshi、Hou Zhaomin
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 56 Issue: 31 Pages: 9207-9210

    • DOI

      10.1002/anie.201705431

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Diastereodivergent Asymmetric Carboamination/Annulation of Cyclopropenes with Aminoalkenes by Chiral Lanthanum Catalysts2017

    • Author(s)
      Teng Huai-Long、Luo Yong、Nishiura Masayoshi、Hou Zhaomin
    • Journal Title

      Journal of the American Chemical Society

      Volume: 139 Issue: 46 Pages: 16506-16509

    • DOI

      10.1021/jacs.7b10786

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Molecular Aggregation States and Physical Properties of Syndiotactic Polystyrene/Hydrogenated Polyisoprene Multiblock Copolymers with Crystalline Hard Domain2017

    • Author(s)
      Higaki Yuji、Suzuki Ken、Kiyoshima Yudai、Toda Tomoyuki、Nishiura Masayoshi、Ohta Noboru、Masunaga Hiroyasu、Hou Zhaomin、Takahara Atsushi
    • Journal Title

      Macromolecules

      Volume: 50 Issue: 16 Pages: 6184-6191

    • DOI

      10.1021/acs.macromol.7b01193

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Heteroatom-assisted olefin polymerization by rare-earth metal catalysts2017

    • Author(s)
      Wang Chunxiang、Luo Gen、Nishiura Masayoshi、Song Guoyong、Yamamoto Atsushi、Luo Yi、Hou Zhaomin
    • Journal Title

      Science Advances

      Volume: 3 Issue: 7 Pages: 1701011-1701011

    • DOI

      10.1126/sciadv.1701011

    • Related Report
      2017 Research-status Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Presentation] Co-syndiospecific Alternating Copolymerization of Functionalized Propylenes and Styrene by Rare-Earth Catalysts2020

    • Author(s)
      Wang Haobing, Yang Yang, Nishiura Masayoshi, Hou Zhaomin
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Scandium-Catalyzed C-H Addition of Pyridines to Heteroatom-Functionalized Internal Alkenes2019

    • Author(s)
      Zhan Gu, Nishiura Masayoshi, Hou Zhaomin
    • Organizer
      第35回希土類討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Rare-Earth-Catalyzed Diastereodivergent [3+2] Annulation of Aldimines with Alkenes via C-H Activation2019

    • Author(s)
      Cong Xuefeng, Nishiura Masayoshi, Hou Zhaomin
    • Organizer
      第35回希土類討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Constructin of All-Carbon Quaternary Stereocenters via Scandium Catalyzed C-H Cyclization of Imidazoles with 1,1- Disubstituted Alkenes2019

    • Author(s)
      Lou Shao-Jie, Mo Zhen-Bo, Nishiura Masayoshi, Hou Zhaomin
    • Organizer
      錯体化学会 第69回討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Rare-Earth-Catalyzed Diastereodivergent [3+2] Annulation of Aldimines with Alkenes via C-H Activation2019

    • Author(s)
      Cong Xuefeng, Nishiura Masayoshi, Hou Zhaomin
    • Organizer
      錯体化学会 第69回討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Scandium-Catalyzed Regio-and Stereoselective Cyclopolymerization of Functionalized Alpha-omega-Dienes and Copolymerization with Ethylene2019

    • Author(s)
      Wang Haobing, Nishiura Masayoshi, Hou Zhaomin
    • Organizer
      第68回高分子討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] Heteroatom-assisted copolymerization of ethylene with functionalized olefins by rare-earth metal catalysts2018

    • Author(s)
      Masayoshi Nishiura
    • Organizer
      The 5th International Symposium on Rare Earth Resource Utilization (ISRERU-5)
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Rare-Earth-Catalyzed C-H Alkylation with Alkenes2018

    • Author(s)
      Yong Luo, Adi Nako, Masayoshi Nishiura, Zhaomin Hou
    • Organizer
      International Conference on Coordination Chemistry, 2018, Sendai, Japan
    • Related Report
      2018 Research-status Report
    • Int'l Joint Research
  • [Presentation] Rare-Earth-Catalyzed C-H Activation for Polymer Synthesis2017

    • Author(s)
      Nishiura M
    • Organizer
      Asian Polyolefin Workshop APO2017
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Rare-Earth-Catalyzed Syndiotactic Polymerization of Styrene Using Pyridines as Chain Transfer Agents2017

    • Author(s)
      Atsushi Yamamoto, Masayoshi Nishiura, Fan Liu, Yi Luo, Zhaomin Hou
    • Organizer
      第66回高分子討論会
    • Related Report
      2017 Research-status Report
  • [Book] 構造制御による革新的ソフトマテリアル創成2018

    • Author(s)
      西浦 正芳, 侯 召民
    • Total Pages
      7
    • Publisher
      化学同人
    • ISBN
      9784759813890
    • Related Report
      2018 Research-status Report
  • [Remarks] 理研研究室ホームページ

    • URL

      http://www.riken.jp/lab-www/organometallic/index.html

    • Related Report
      2019 Annual Research Report 2018 Research-status Report 2017 Research-status Report
  • [Remarks] 理研侯有機金属化学研究室ホームページ

    • URL

      http://www.riken.jp/research/labs/chief/organometal_chem/

    • Related Report
      2019 Annual Research Report 2018 Research-status Report 2017 Research-status Report
  • [Remarks] 環境資源科学研究センター 先進機能触媒研究グループホームページ

    • URL

      http://www.riken.jp/research/labs/csrs/adv_catal/

    • Related Report
      2019 Annual Research Report 2018 Research-status Report 2017 Research-status Report
  • [Remarks] RIKEN public website-english

    • URL

      http://www.riken.jp/en/research/labs/chief/organometal_chem/

    • Related Report
      2018 Research-status Report 2017 Research-status Report
  • [Patent(Industrial Property Rights)] 極性オレフィン系重合体からなる成形品とその物性2018

    • Inventor(s)
      Yang Yang, 王号兵、西浦正芳、侯召民
    • Industrial Property Rights Holder
      Yang Yang, 王号兵、西浦正芳、侯召民
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2018-046829
    • Filing Date
      2018
    • Related Report
      2017 Research-status Report
  • [Patent(Industrial Property Rights)] 極性オレフィン重合体及び共重合体の製造方法2018

    • Inventor(s)
      王 春翔、王号兵、Yang Yang, 西浦正芳、侯召民
    • Industrial Property Rights Holder
      王 春翔、王号兵、Yang Yang, 西浦正芳、侯召民
    • Industrial Property Rights Type
      特許
    • Filing Date
      2018
    • Related Report
      2017 Research-status Report
    • Overseas

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Published: 2017-04-28   Modified: 2021-02-19  

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