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Investigation on reaction mechanism in the transition state of bifunctional chiral metal nanoparticle catalysts

Research Project

Project/Area Number 15KT0058
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeMulti-year Fund
Section特設分野
Research Field Transition State Control
Research InstitutionThe University of Tokyo

Principal Investigator

Miyamura Hiroyuki  東京大学, 大学院理学系研究科(理学部), 助教 (00548943)

Project Period (FY) 2015-07-10 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥17,940,000 (Direct Cost: ¥13,800,000、Indirect Cost: ¥4,140,000)
Fiscal Year 2017: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2016: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000)
Fiscal Year 2015: ¥9,620,000 (Direct Cost: ¥7,400,000、Indirect Cost: ¥2,220,000)
Keywords不斉合成 / キラル金属ナノ粒子 / 遷移状態 / 反応機構研究 / 二機能性触媒 / キラル配位子 / 不斉1,4-付加反応 / 不均一系触媒 / 不斉1,4付加反応 / キラルジエン配位子 / 高機能触媒 / 反応機構解明 / 固相触媒 / 反応機構解析 / ロジウム
Outline of Final Research Achievements

Chiral metal nanoparticle catalysts of bifunctional chiral ligand and Rh-Ag nanoparticles mediate asymmetric 1,4-addition of aryl boronic acid to unsaturated carbonyl compounds in high yield and enantioselectivity. We hypothesized that the diene structure of the ligand construct asymmetric environment through interaction with active metal species and the secondary amide moiety places substrate in appropriate position in the reaction environment through hydrogen bonding. According to kinetic studies, XPS analysis, SR-MAS NMR analysis, and non-linear effect analysis provided various information about the active metal species, fashion of interaction between active metal species and chiral ligand, and transition states of intermediates in the catalytic cycles.

Report

(4 results)
  • 2017 Annual Research Report   Final Research Report ( PDF )
  • 2016 Research-status Report
  • 2015 Research-status Report
  • Research Products

    (31 results)

All 2018 2017 2016 2015 Other

All Int'l Joint Research (1 results) Journal Article (12 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 12 results,  Open Access: 3 results,  Acknowledgement Compliant: 10 results) Presentation (14 results) (of which Int'l Joint Research: 5 results,  Invited: 3 results) Remarks (4 results)

  • [Int'l Joint Research] University of Sheffield(英国)

    • Related Report
      2017 Annual Research Report
  • [Journal Article] Rhodium-catalyzed asymmetric 1,4-addition reactions of aryl boronic acids with nitroalkenes: reaction mechanism and development of homogeneous and heterogeneous catalysts2017

    • Author(s)
      Miyamura, H.; Nishino, K.; Yasukawa, T.; Kobayashi, S.
    • Journal Title

      Chemical Science

      Volume: 8 Issue: 12 Pages: 8362-8372

    • DOI

      10.1039/c7sc03025h

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Water as a catalytic switch in the oxidation of aryl alcohols by polymer incarcerated rhodium nanoparticles.2017

    • Author(s)
      Weston, Jack O.; Miyamura, Hiroyuki; Yasukawa, Tomohiro; Sutarma, Dedi; Baker, Chloe A.; Singh, Preabjot K.; Bravo-Sanchez, Mariela; Sano, Naoko; Cumpson, Peter J.; Ryabenkova, Yulia; Kobayashi, Shu; Conte, Marco,
    • Journal Title

      Catalysis Science & Technology

      Volume: 7 Issue: 18 Pages: 3985-3998

    • DOI

      10.1039/c7cy01006k

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Asymmetric Arylation of Imines Catalyzed by Heterogeneous Chiral Rhodium Nanoparticles.2016

    • Author(s)
      Yasukawa, Tomohiro; Kuremoto, Tatsuya; Miyamura, Hiroyuki; Kobayashi, Shu
    • Journal Title

      Org. Lett.

      Volume: 18 Issue: 11 Pages: 2716-2718

    • DOI

      10.1021/acs.orglett.6b01172

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Chiral Ligand-Modified Metal Nanoparticles as Unique Catalysts for Asymmetric C-C Bond-Forming Reactions: How Are Active Species Generated?2016

    • Author(s)
      Yasukawa, Tomohiro; Miyamura, Hiroyuki; Kobayashi, Shu
    • Journal Title

      ACS Catalysis

      Volume: 6 Issue: 11 Pages: 7979-7988

    • DOI

      10.1021/acscatal.6b02446

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] N-Heterocyclic Carbene Coordinated Heterogeneous Pd Nanoparticles as Catalysts for Suzuki-Miyaura Coupling.2016

    • Author(s)
      Min, Hyemin; Miyamura, Hiroyuki; Kobayashi, Shu
    • Journal Title

      Chem. Lett.

      Volume: 45 Issue: 7 Pages: 837-839

    • DOI

      10.1246/cl.160369

    • NAID

      130005253033

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Integrated Process of Aerobic Oxidation-Olefination-Asymmetric C-C Bond Formation Catalyzed by Robust Heterogeneous Gold/Palladium and Chirally Modified Rhodium Nanoparticles.2015

    • Author(s)
      Miyamura, H.; Suzuki, A.; Yasukawa, T.; Kobayashi, S.
    • Journal Title

      Advanced Synthesis & Catalysis

      Volume: 357 Issue: 18 Pages: 3815-3819

    • DOI

      10.1002/adsc.201500529

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Chiral Metal Nanoparticle Systems as Heterogeneous Catalysts beyond Homogeneous Metal Complex Catalysts for Asymmetric Addition of Arylboronic Acids to alpha,beta-Unsaturated Carbonyl Compounds.2015

    • Author(s)
      Yasukawa, T.; Suzuki, A.; Miyamura, H.; Nishino, K.; Kobayashi, S.
    • Journal Title

      Journal of the American Chemical Society

      Volume: 137 Issue: 20 Pages: 6616-6623

    • DOI

      10.1021/jacs.5b02213

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Cellulose-supported chiral rhodium nanoparticles as sustainable heterogeneous catalysts for asymmetric carbon-carbon bond-forming reactions.2015

    • Author(s)
      Yasukawa, T.; Miyamura, H.; Kobayashi, S.
    • Journal Title

      Chemical Science

      Volume: 6 Issue: 11 Pages: 6224-6229

    • DOI

      10.1039/c5sc02510a

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Self-Assembled Nanocomposite Organic Polymers with Aluminum and Scandium as Heterogeneous Water-Compatible Lewis Acid Catalysts.2015

    • Author(s)
      Miyamura, H.; Sonoyama, A.; Hayrapetyan, D.; Kobayashi, S.
    • Journal Title

      Angewandte Chemie-International Edition

      Volume: 54 Issue: 36 Pages: 10559-10563

    • DOI

      10.1002/anie.201503874

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Size of Gold Nanoparticles Driving Selective Amide Synthesis through Aerobic Condensation of Aldehydes and Amines2015

    • Author(s)
      Miyamura, H.; Min, H.; Soule, J.-F.; Kobayashi, S.
    • Journal Title

      Angewandte Chemie-International Edition

      Volume: 54 Issue: 26 Pages: 7564-7567

    • DOI

      10.1002/anie.201501795

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Powerful Continuous-Flow Hydrogenation by using Poly(dimethyl)silane-Supported Palladium Catalysts2015

    • Author(s)
      Kobayashi, S.; Okumura, M.; Akatsuka, Y.; Miyamura, H.; Ueno, M.; Oyamada, H.
    • Journal Title

      Chemcatchem

      Volume: 7 Issue: 24 Pages: 4025-4029

    • DOI

      10.1002/cctc.201500973

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synergistic cascade catalysis by metal nanoparticles and Lewis acids in hydrogen autotransfer2015

    • Author(s)
      Choo, G. C. Y.; Miyamura, H.; Kobayashi, S.
    • Journal Title

      Chem. Sci.

      Volume: 6 Issue: 3 Pages: 1719-1727

    • DOI

      10.1039/c4sc03627a

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Presentation] Development of heterogeneous metal nanoparticle catalysts toward continuous-flow reactions2018

    • Author(s)
      宮村浩之
    • Organizer
      The first international conference on automated flow and microreactor synthesis (ICAMS-1)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] キラルロジウムナノ粒子触媒を用いたアリールボロン酸のβ,γ-不飽和-αケトエステルへの不斉1,4-付加反応2018

    • Author(s)
      宮村浩之,小林修
    • Organizer
      日本化学会98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] ポリシラン固定化金属ナノ粒子触媒を用いたアニリンおよびニトロアレン誘導体とアルキルアミンとの還元的アミノ化反応2018

    • Author(s)
      鈴木綾,宮村浩之,小林修
    • Organizer
      日本化学会98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Development of Chiral Ligand Immobilized Heterogeneous Rh Nanoparticle Catalysts and Application to Flow Systems2018

    • Author(s)
      ミンヘミン,宮村浩之,安川知宏,西野浩平,小林修
    • Organizer
      日本化学会98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Hydrogenation of Aromatic Compounds Using Polymer Immobilized Metal Nanoparticle Catalysts2017

    • Author(s)
      MIYAMURA, Hiroyuki; SUZUKI, Aya; KOBAYASHI, Shu;
    • 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] 配位子固定化不均一系キラルロジウムナノ粒子触媒の開発と1,4-付加反応への応用2017

    • Author(s)
      MIN Hyemin・宮村 浩之・西野 浩平・小林 修
    • 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] 金属ナノ粒子が拓く環境に優しい化学とフロー合成2017

    • Author(s)
      宮村浩之
    • Organizer
      化学フェスタ2017 「中分子戦略」特別企画:「中分子」に託そう,分子科学の未来を!
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] Heterogeneous Rhodium Nanoparticle Catalyzed Asymmetric 1,4-Addition of Aryl Boronic Acids to Nitroalkenes and α,β-Unsaturated Carbonyl Compounds2017

    • Author(s)
      Hiroyuki Miyamura, Kohei Nishino, Tomohiro Yasukawa, Shu Kobayashi
    • Organizer
      3rd International Symposium on Middle Molecular Strategy (ISMMS-3) & ISONIS-11
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 芳香族化合物の高効率水素化反応に有効な不均一系金属ナノ粒子触媒の開発2016

    • Author(s)
      鈴木 綾,宮村 浩之,安川 知宏,小林 修
    • Organizer
      第110回有機合成シンポジウム2016年【秋】
    • Place of Presentation
      早稲田大学国際会議場 (東京都新宿区)
    • Year and Date
      2016-11-10
    • Related Report
      2016 Research-status Report
  • [Presentation] 有機高分子,スカンジウム,およびアルミニウム還元剤の自己組織化により形成する不均一系Lewis酸触媒の開発2016

    • Author(s)
      宮村浩之,小林 修
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学 京田辺キャンパス 京田辺市,京都府
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] 不均一系金属ナノ粒子触媒を用いる有機合成反応の開発 ー反応集積化と不斉合成への展開ー2016

    • Author(s)
      宮村 浩之
    • Organizer
      関西学院大学大学院理工学研究科 機能性ナノ単一サイズ有機分子創製研究 パイスター分子制御による未来型物質変換研究拠点 2016年度 合同シンポジウム
    • Place of Presentation
      関西学院大学 神戸三田キャンパス (兵庫県三田市)
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] Integration of aerobic oxidation of alcohols and unsaturated bond formation catalyzed by polymer-incarcerated metal nanoparticle catalysts2015

    • Author(s)
      Suzuki, A.; Miyamura, H.; Yasukawa, T.; Kobayashi, S.
    • Organizer
      Pacifichem2015
    • Place of Presentation
      Hawaii Convention Center Honolulu, USA
    • Year and Date
      2015-12-16
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Heterogeneous metal nanoparticle catalysts for multiphase flow processes2015

    • Author(s)
      Miyamura, H.; Kobayashi, S.
    • Organizer
      Pacifichem2015
    • Place of Presentation
      Hilton Hawaiian Village Honolulu, USA
    • Year and Date
      2015-12-16
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Development of Heterogeneous Chiral Rh Nanoparticles for Asymmetric C-C Bond Forming Reactions2015

    • Author(s)
      Yasukawa, T.; Miyamura, H.; Kobayashi, S.
    • Organizer
      17th International Symposium on Relations between Homogeneous and Heterogeneous Catalysis
    • Place of Presentation
      Educatorium (University Campus 'De Uithof'), Leuvenlaan 19, 3584 CE, Utrecht, The Netherlands
    • Year and Date
      2015-07-13
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Remarks] 東京大学大学院理学系研究科化学専攻/有機合成化学研究室

    • URL

      http://www.chem.s.u-tokyo.ac.jp/users/synorg/index.html

    • Related Report
      2017 Annual Research Report
  • [Remarks] 東京大学大学院理学系研究科/有機合成化学研究室

    • URL

      http://www.chem.s.u-tokyo.ac.jp/users/synorg/index.html

    • Related Report
      2016 Research-status Report
  • [Remarks] literature | 文献 | 東京大学大学院理学系研究科/有機合成化学研究室

    • URL

      http://www.chem.s.u-tokyo.ac.jp/users/synorg/jp/literature/info_2015.html

    • Related Report
      2015 Research-status Report
  • [Remarks] literature | 文献 | 東京大学大学院理学系研究科/有機合成化学研究室

    • URL

      http://www.chem.s.u-tokyo.ac.jp/users/synorg/en/literature/info_2015.html

    • Related Report
      2015 Research-status Report

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Published: 2015-07-14   Modified: 2022-08-29  

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