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Catalyst design and challenging molecular transformations for advanced utilization of first-row transition metals

Research Project

Project/Area Number 17H04877
Research Category

Grant-in-Aid for Young Scientists (A)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionThe University of Tokyo (2020-2022)
Hokkaido University (2017-2019)

Principal Investigator

Iwai Tomohiro  東京大学, 大学院総合文化研究科, 講師 (30610729)

Project Period (FY) 2017-04-01 – 2022-03-31
Project Status Completed (Fiscal Year 2022)
Budget Amount *help
¥23,920,000 (Direct Cost: ¥18,400,000、Indirect Cost: ¥5,520,000)
Fiscal Year 2020: ¥3,900,000 (Direct Cost: ¥3,000,000、Indirect Cost: ¥900,000)
Fiscal Year 2019: ¥8,580,000 (Direct Cost: ¥6,600,000、Indirect Cost: ¥1,980,000)
Fiscal Year 2018: ¥6,630,000 (Direct Cost: ¥5,100,000、Indirect Cost: ¥1,530,000)
Fiscal Year 2017: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Keywords第一周期遷移金属 / 不均一系触媒 / 均一系触媒 / ホスフィン / ビピリジン / カップリング / 拡張π共役系 / 可視光レドックス触媒 / メタラフォトレドックス触媒 / シクロデキストリン / 連結型ロタキサン / ポリスチレン / 触媒 / 配位子 / ニッケル / 交差求電子剤カップリング / フッ化アリール / ホスフィンオキシド / 芳香族求核置換反応 / 固定化 / ビスホスフィン / イリジウム / 水素移動型還元反応 / 脱水素化反応 / 銅 / 酸フッ化物 / クロスカップリング / 触媒設計
Outline of Final Research Achievements

Aiming at the advanced utilization of first-row transition metals in organic synthesis, we developed highly active catalysts based on designing reaction fields that take advantage of the properties of solids and molecules. With heterogeneous nickel catalysts consisting of polystyrene-cross-linking bisphosphine PS-DPPBz that allowed selective metal monochelation, efficient molecular transformations such as cross-coupling of aryl chlorides with alkyl lithiums and decarboxylation of aryl carbamates for aniline synthesis were developed. Moreover, we designed and synthesized dumbbell-shaped bipyridine ligands that promotes nickel-catalyzed one-electron transfer coupling, and their utilities were demonstrated in cross-electrophilic coupling between aryl bromides and alkyl bromides.

Academic Significance and Societal Importance of the Research Achievements

第一周期遷移金属は地球上に豊富に存在することから、環境調和型有機合成の観点で魅力的であるが、凝集や不均化によって失活しやすく、その利用には制限があった。本研究では、固体や分子の特性を活かした反応場設計に基づく第一周期遷移金属触媒の高活性化を達成し、既存系を凌駕する高効率反応や新規分子変換反応の開発に成功した。本成果は、物質生産技術の基礎となる有機合成化学・触媒化学分野の一層の発展に寄与するものである。

Report

(6 results)
  • 2022 Final Research Report ( PDF )
  • 2021 Annual Research Report
  • 2020 Annual Research Report
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • 2017 Annual Research Report
  • Research Products

    (35 results)

All 2022 2021 2020 2019 2018 2017 Other

All Journal Article (12 results) (of which Peer Reviewed: 12 results,  Open Access: 2 results) Presentation (20 results) (of which Int'l Joint Research: 4 results,  Invited: 15 results) Remarks (2 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Irradiation with UV Light Accelerates the Migita?Kosugi?Stille Coupling Reaction in Air2022

    • Author(s)
      Ishikawa Takumi、Murata Mako、Masai Hiroshi、Iwai Tomohiro、Terao Jun
    • Journal Title

      Chemistry Letters

      Volume: 51 Issue: 2 Pages: 124-126

    • DOI

      10.1246/cl.210665

    • NAID

      130008161615

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] A Hollow-shaped Caged Triarylphosphine: Synthesis, Characterization and Applications to Gold(I)-catalyzed 1,8-Enyne Cycloisomerization2021

    • Author(s)
      Iwai Tomohiro、Goto Yuto、You Zhensheng、Sawamura Masaya
    • Journal Title

      Chemistry Letters

      Volume: 50 Issue: 6 Pages: 1236-1239

    • DOI

      10.1246/cl.210176

    • NAID

      130008053391

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Phosphinylation of Non‐activated Aryl Fluorides through Nucleophilic Aromatic Substitution at the Boundary of Concerted and Stepwise Mechanisms2021

    • Author(s)
      You Zhensheng、Higashida Kosuke、Iwai Tomohiro、Sawamura Masaya
    • Journal Title

      Angewandte Chemie International Edition

      Volume: 60 Issue: 11 Pages: 5778-5782

    • DOI

      10.1002/anie.202013544

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Dumbbell‐Shaped 2,2’‐Bipyridines: Controlled Metal Monochelation and Application to Ni‐Catalyzed Cross‐Couplings2020

    • Author(s)
      Kim Yongjoon、Iwai Tomohiro、Fujii Sho、Ueno Kosei、Sawamura Masaya
    • Journal Title

      Chemistry ? A European Journal

      Volume: 27 Issue: 7 Pages: 2289-2293

    • DOI

      10.1002/chem.202004053

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Ir-Catalyzed Reversible Acceptorless Dehydrogenation/Hydrogenation of N-Substituted and Unsubstituted Heterocycles Enabled by a Polymer-Cross-Linking Bisphosphine2020

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

      Organic Letters

      Volume: 22 Issue: 13 Pages: 5240-5245

    • DOI

      10.1021/acs.orglett.0c01905

    • NAID

      120007053061

    • Related Report
      2020 Annual Research Report
    • 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 Issue: 15 Pages: 5867-5872

    • DOI

      10.1021/acs.orglett.9b01989

    • NAID

      120006869882

    • Related Report
      2019 Annual Research Report
    • 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 Issue: 40 Pages: 9410-9414

    • DOI

      10.1002/chem.201900822

    • NAID

      120006844535

    • Related Report
      2018 Annual Research Report
    • 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 Issue: 18 Pages: 7261-7265

    • DOI

      10.1021/jacs.9b02751

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A Polystyrene‐Cross‐Linking Tricyclohexylphosphine: Synthesis, Characterization and Applications to Pd‐Catalyzed Cross‐Coupling Reactions of Aryl Chlorides2019

    • Author(s)
      Arashima Junya、Iwai Tomohiro、Sawamura Masaya
    • Journal Title

      Chemistry - An Asian Journal

      Volume: 14 Issue: 3 Pages: 411-415

    • DOI

      10.1002/asia.201801651

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Heterogeneous Nickel‐Catalyzed Cross‐Coupling between Aryl Chlorides and Alkyllithiums Using a Polystyrene‐Cross‐Linking Bisphosphine Ligand2019

    • Author(s)
      Yamazaki Yuki、Arima Nozomi、Iwai Tomohiro、Sawamura Masaya
    • Journal Title

      Advanced Synthesis & Catalysis

      Volume: 361 Issue: 10 Pages: 2250-2254

    • DOI

      10.1002/adsc.201801713

    • NAID

      120006798317

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Nickel-catalyzed amination of aryl fluorides with primary amines2018

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

      Chemical Communications

      Volume: 54 Issue: 14 Pages: 1718-1721

    • DOI

      10.1039/c7cc08181b

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Polystyrene-Cross-Linking Ortho-Substituted Triphenylphosphines: Synthesis, Coordination Properties, and Application to Pd-Catalyzed Cross-Coupling of Aryl Chlorides2017

    • Author(s)
      Tomohiro Iwai, Kiichi Asano, Tomoya Harada, Masaya Sawamura
    • Journal Title

      Bulletine of Chemical Society of Japan

      Volume: 90 Issue: 8 Pages: 943-949

    • DOI

      10.1246/bcsj.20170141

    • NAID

      130005973622

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Presentation] 固体材料と金属錯体のハイブリッド化による機能性不均一系触媒の開発2022

    • Author(s)
      岩井智弘
    • Organizer
      ハイブリッド触媒 若手道場Online
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] 固体-分子ハイブリッド系による触媒デザイン2022

    • Author(s)
      岩井智弘
    • Organizer
      第130回触媒討論会
    • Related Report
      2021 Annual Research Report
    • Invited
  • [Presentation] 連結型ロタキサン構造を有する被覆π共役ビピリジン-金属錯体の合成と光物性2022

    • Author(s)
      安部慎祐・宮岸拓路・正井宏・滝沢進也・岩井智弘・寺尾潤
    • Organizer
      日本化学会第103春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] 連結型ロタキサン構造を有する窒素系二座配位子の合成2021

    • Author(s)
      安部 慎祐・宮岸 拓路・正井 宏・岩井 智弘・寺尾 潤
    • Organizer
      日本化学会第102春季年会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Acceleration Effect of Migita-Kosugi-Stille Coupling Reaction by UV-Irradiation2021

    • Author(s)
      Takumi Ishikawa, Mako Murata, Hiroshi Masai, Tomohiro Iwai, Jun Terao
    • Organizer
      The 2021 International Chemical Congress of Pacific Basin Societies (Pacifichem)
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 固相多点担持ホスフィン配位子の設計・合成・触媒機能2021

    • Author(s)
      岩井智弘
    • Organizer
      日本化学会 第101春季年会 若い世代の特別講演会(オンライン)
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] 固体および分子の空間特性を活かした遷移金属錯体触媒の設計2021

    • Author(s)
      岩井智弘
    • Organizer
      第37回有機合成化学セミナー(オンライン)
    • Related Report
      2020 Annual Research Report
    • Invited
  • [Presentation] シリカまたはポリスチレンと第3級ホスフィンの機能融合に基づく金属錯体触媒の設計2019

    • Author(s)
      岩井智弘
    • Organizer
      第23回ケイ素化学協会シンポジウム
    • Related Report
      2019 Annual Research Report
    • Invited
  • [Presentation] Multipoint Solid-Supported Phosphine Ligands for Active Site Isolation2019

    • Author(s)
      Tomohiro Iwai
    • Organizer
      Hokkaido mini-Symposium by Young Generations in Asia
    • Related Report
      2019 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 固体と分子の融合による触媒デザイン2019

    • Author(s)
      岩井智弘
    • Organizer
      第52回有機金属若手の会 夏の学校
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] 空間制御に基づく配位子設計と触媒開発2019

    • Author(s)
      岩井智弘
    • Organizer
      分子環境相関論オータムセミナー2019
    • Related Report
      2018 Annual Research Report
    • Invited
  • [Presentation] 触媒の可能性を拓く反応場デザイン2019

    • Author(s)
      岩井智弘
    • Organizer
      第86回フロンティア材料研究所講演会「高機能材料・触媒による反応場制御」
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] ポリスチレン架橋ビスホスフィン配位子を用いたニッケル触媒村橋カップリング反応2018

    • Author(s)
      岩井智弘・山﨑勇輝・有馬望・澤村正也
    • Organizer
      第122回触媒討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 配位子づくりに魅せられて;金属錯体反応場の精密設計に基づく触媒機能の創出2018

    • Author(s)
      岩井智弘
    • Organizer
      平成30年度第1回有機金属若手研究者の会
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] Multipoint Solid-Supported Phosphine Ligands for Efficient Organometallic Catalysis2018

    • Author(s)
      Tomohiro Iwai
    • Organizer
      日本化学会 第98春季年会 (2018) アジア国際シンポジウム
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 反応場の特性を活かした高活性金属錯体触媒の設計2018

    • Author(s)
      岩井智弘
    • Organizer
      平成29年度 日本化学会北海道支部奨励賞 受賞講演
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] 固相担体の特性を活かした高活性金属錯体触媒の創製2017

    • Author(s)
      岩井智弘
    • Organizer
      2017年度 触媒学会北海道支部 札幌講演会
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] 固相多点担持法による高活性金属錯体触媒の設計開発2017

    • Author(s)
      岩井智弘
    • Organizer
      第1回産総研化学研究シンポジウム「夢見る30代化学者たちの挑戦」
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] 第一級アミンによるフッ化アリールのニッケル触媒アミノ化反応2017

    • Author(s)
      岩井智弘・原田友哉・澤村正也
    • Organizer
      第120回触媒討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Polystyrene-Cross-Linking Phosphine Ligands for Producing Highly Active Metal Catalysts2017

    • Author(s)
      Tomohiro Iwai
    • Organizer
      International Symposium on Pure & Applied Chemistry (ISPAC) 2017
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / 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

    • URL

      https://wwwchem.sci.hokudai.ac.jp/~orgmet/index.php?id=1

    • Related Report
      2019 Annual Research Report 2018 Annual Research Report
  • [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

    • URL

      https://wwwchem.sci.hokudai.ac.jp/~orgmet/index.php?id=1

    • Related Report
      2017 Annual Research Report
  • [Patent(Industrial Property Rights)] ビピリジン骨格を有する配位子、それを含む錯体及びそれを含む触媒2020

    • Inventor(s)
      澤村正也,岩井智弘,金容俊
    • Industrial Property Rights Holder
      澤村正也,岩井智弘,金容俊
    • Industrial Property Rights Type
      特許
    • Filing Date
      2020
    • Related Report
      2020 Annual Research Report

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Published: 2017-04-28   Modified: 2024-01-30  

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