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2019 Fiscal Year Annual Research Report

Development of Highly Active Transition Metal Catalysts Based on Solid Support Strategies

Planned Research

Project AreaPrecise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions
Project/Area Number 15H05801
Research InstitutionHokkaido University

Principal Investigator

澤村 正也  北海道大学, 理学研究院, 教授 (40202105)

Project Period (FY) 2015-06-29 – 2020-03-31
Keywords触媒設計 / ホスフィン / ポリスチレン / 固相担持 / 架橋剤 / ニッケル / 有機リチウム / アミノ化
Outline of Annual Research Achievements

分離・再利用が容易な高分子固定化金属触媒による合成プロセスの効率化が期待される。しかし、高分子鎖の立体障害に起因する触媒活性の低下がしばしば問題となる。我々は、複数の重合部位を有するホスフィン分子を高分子架橋剤とすることで金属配位点を空間的に孤立化させて高活性金属種を生成する手法を開発した。単座ホスフィンを3点架橋剤として得られるPS-TPPや2座ホスフィン配位子を4点架橋剤とするPS-DPPBzが代表例である。
ポリスチレン4点架橋ビスホスフィンPS-DPPBzの応用に関して、O-アリールカルバメートのニッケル触媒脱炭酸反応によるアニリン類の合成の成果(大阪大学鳶巣教授、本領域A01班)に関して論文発表を行った。また、1,4-ジオキサンを水素源とするイリジウム触媒によるアルケンの水素化反応におけるPS-DPPBzの効果についても論文発表を行うとともに、PS-DPPBz-イリジウム触媒による含窒素ヘテロ環の脱水素化反応に関しても成果をまとめ論文投稿を行った。
九州大学三浦教授との共同研究によりポリスチレン3点架橋ホスフィンPS-TPPのモノリスの作製法を開発し、パラジウム触媒によるアリールボロン酸と塩化アリールのクロスカップリング(鈴木―宮浦カップリング)のフロー反応を実現し、その成果の一部について論文発表を行った。キラルビスホスフィンを架橋剤とするポリスチレン卿重合体の合成とその錯体化についても検討し、進捗があった。
配位子の空間的孤立化の概念を不斉配位子の開発に展開させて均一系キラルモノホスファイト配位子設計し、イリジウムおよびロジウム触媒による不活性C(sp3)-H結合の不斉ホウ素化反応に応用し、その成果を2報の論文として発表した。

Research Progress Status

令和元年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

令和元年度が最終年度であるため、記入しない。

  • Research Products

    (22 results)

All 2020 2019 Other

All Journal Article (9 results) (of which Peer Reviewed: 9 results,  Open Access: 1 results) Presentation (10 results) (of which Int'l Joint Research: 8 results,  Invited: 10 results) Remarks (2 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Copper-catalyzed enantioselective conjugate reduction of α,β-unsaturated esters with chiral phenol?carbene ligands2020

    • Author(s)
      Mimura Shohei、Mizushima Sho、Shimizu Yohei、Sawamura Masaya
    • Journal Title

      Beilstein Journal of Organic Chemistry

      Volume: 16 Pages: 537~543

    • DOI

      10.3762/bjoc.16.50

    • Peer Reviewed / Open Access
  • [Journal Article] Polystyrene‐Supported PPh3 in Macroporous Monolith: Effect of Cross‐Linking Degree on Coordination Mode and Catalytic Activity in Pd‐Catalyzed C‐C Cross‐Coupling of Aryl Chlorides2020

    • Author(s)
      Matsumoto Hikaru、Hoshino Yu、Iwai Tomohiro、Sawamura Masaya、miura yoshiko
    • Journal Title

      ChemCatChem

      Volume: 12 Pages: in press

    • DOI

      10.1002/cctc.202000651

    • Peer Reviewed
  • [Journal Article] Asymmetric Synthesis of α-Alkylidene-β-Lactams through Copper Catalysis with a Prolinol-Phosphine Chiral Ligand2019

    • Author(s)
      Imai Koji、Takayama Yurie、Murayama Hiroaki、Ohmiya Hirohisa、Shimizu Yohei、Sawamura Masaya
    • Journal Title

      Organic Letters

      Volume: 21 Pages: 1717~1721

    • DOI

      10.1021/acs.orglett.9b00276

    • Peer Reviewed
  • [Journal Article] Nickel‐Copper‐Catalyzed Hydroacylation of Vinylarenes with Acyl Fluorides and Hydrosilanes2019

    • Author(s)
      Ueda Yusuke、Iwai Tomohiro、Sawamura Masaya
    • Journal Title

      Chemistry - A European Journal

      Volume: 25 Pages: 9410~9414

    • DOI

      10.1002/chem.201900822

    • Peer Reviewed
  • [Journal Article] Iridium-Catalyzed Asymmetric Borylation of Unactivated Methylene C(sp3)-H Bonds2019

    • Author(s)
      Reyes Ronald L.、Iwai Tomohiro、Maeda Satoshi、Sawamura Masaya
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Pages: 6817~6821

    • DOI

      10.1021/jacs.9b01952

    • Peer Reviewed
  • [Journal Article] Nickel-Catalyzed Decarboxylation of Aryl Carbamates for Converting Phenols into Aromatic Amines2019

    • Author(s)
      Nishizawa Akihiro、Takahira Tsuyoshi、Yasui Kosuke、Fujimoto Hayato、Iwai Tomohiro、Sawamura Masaya、Chatani Naoto、Tobisu Mamoru
    • Journal Title

      Journal of the American Chemical Society

      Volume: 141 Pages: 7261~7265

    • DOI

      10.1021/jacs.9b02751

    • Peer Reviewed
  • [Journal Article] Iridium-Catalyzed Alkene-Selective Transfer Hydrogenation with 1,4-Dioxane as Hydrogen Donor2019

    • Author(s)
      Zhang Deliang、Iwai Tomohiro、Sawamura Masaya
    • Journal Title

      Organic Letters

      Volume: 21 Pages: 5867~5872

    • DOI

      10.1021/acs.orglett.9b01989

    • Peer Reviewed
  • [Journal Article] Boron-Catalyzed α-Amination of Carboxylic Acids2019

    • Author(s)
      Morisawa Takuto、Sawamura Masaya、Shimizu Yohei
    • Journal Title

      Organic Letters

      Volume: 21 Pages: 7466~7469

    • DOI

      10.1021/acs.orglett.9b02769

    • Peer Reviewed
  • [Journal Article] Asymmetric Synthesis of α-Aminoboronates via Rhodium-Catalyzed Enantioselective C(sp3)-H Borylation2019

    • Author(s)
      Reyes Ronald L.、Sato Miyu、Iwai Tomohiro、Sawamura Masaya
    • Journal Title

      Journal of the American Chemical Society

      Volume: 142 Pages: 589~597

    • DOI

      10.1021/jacs.9b12013

    • Peer Reviewed
  • [Presentation] Ligand-Enabled Selective Borylation of C(sp2)-H and C(sp3)-H Bonds2019

    • Author(s)
      Masaya Sawamura
    • Organizer
      The 27th French-Japanese Symposium on Medicinal and Fine Chemistry
    • Int'l Joint Research / Invited
  • [Presentation] Enantioselective Methylene C(sp3)-H Borylation2019

    • Author(s)
      Masaya Sawamura
    • Organizer
      The 47th Naito Conference on "C-H Activation and Transformation"
    • Int'l Joint Research / Invited
  • [Presentation] Asymmetric Synthesis of α-Aminoalkylboronates through Rh-Catalyzed Enantioselective C(sp3)-H Borylation2019

    • Author(s)
      Masaya Sawamura, Ronald Reyes, Tomohiro Iwai, Satoshi Maeda
    • Organizer
      20th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS20)
    • Invited
  • [Presentation] Catalytic Enantioselective C(sp3)-H Borylation2019

    • Author(s)
      Masaya Sawamura
    • Organizer
      7th Latin American Symposium on Coordination and Organometallic Chemistry
    • Int'l Joint Research / Invited
  • [Presentation] Noncovalent Interactions in Ir-Catalyzed Enantioselective C(sp3-H Borylation2019

    • Author(s)
      Masaya Sawamura
    • Organizer
      1st International Conferences on Noncovalent Interactions (ICNI-2019)
    • Int'l Joint Research / Invited
  • [Presentation] Catalytic Enantioselective C(sp3)-H Borylation: Mechanism and Applications2019

    • Author(s)
      Masaya Sawamura
    • Organizer
      The 9th Junior International Conference on Cutting-Edge Organic Chemistry in Asia (Junior ICCEOCA-9)
    • Int'l Joint Research / Invited
  • [Presentation] Ligand-Enabled Selective Borylation of C(sp2)-H and C(sp3)-H Bonds2019

    • Author(s)
      Masaya Sawamura
    • Organizer
      NOST Organic Chemistry & Biomolecular Chemistry Conference
    • Int'l Joint Research / Invited
  • [Presentation] Catalytic Enantioselective C(sp3)-H Borylation2019

    • Author(s)
      Masaya Sawamura
    • Organizer
      The 2nd ICReDD International Symposium
    • Int'l Joint Research / Invited
  • [Presentation] Asymmetric Synthesis of α-Aminoboronates via Rhodium-Catalyzed Enantioselective C(sp3)-H Borylation2019

    • Author(s)
      Masaya Sawamura
    • Organizer
      The 2nd Japan Germany Singapore Trilateral Symposium on Precision Synthesis and Catalysis
    • Int'l Joint Research / Invited
  • [Presentation] Experimantal and Computational Approach to Innovatve Asymmetric C-H Functionalization2019

    • Author(s)
      Masaya Sawamura
    • Organizer
      MANA Seminar
    • Invited
  • [Remarks] 北海道大学大学院理学研究院化学部門 有機金属化学研究室 ホームページ

    • URL

      https://wwwchem.sci.hokudai.ac.jp/~orgmet/

  • [Remarks] Organometallic Chemistry Lab. Home Page

    • URL

      https://wwwchem.sci.hokudai.ac.jp/~orgmet/index.php?id=25

  • [Patent(Industrial Property Rights)] 新規な多孔性架橋ポリマー、それを用いた固定化触媒および装置2020

    • Inventor(s)
      松本光,三浦佳子,星野友,澤村正也,岩井智弘,石川真一
    • Industrial Property Rights Holder
      松本光,三浦佳子,星野友,澤村正也,岩井智弘,石川真一
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      特願 2020-031870

URL: 

Published: 2021-12-27  

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