• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Development of Efficient Organic Synthesis Utilizing C-C Bond Cleavage Reactions

Research Project

Project/Area Number 18H01981
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Review Section Basic Section 33020:Synthetic organic chemistry-related
Research InstitutionNagasaki University

Principal Investigator

KIMURA Masanari  長崎大学, 工学研究科, 教授 (10274622)

Project Period (FY) 2018-04-01 – 2021-03-31
Project Status Completed (Fiscal Year 2020)
Budget Amount *help
¥17,290,000 (Direct Cost: ¥13,300,000、Indirect Cost: ¥3,990,000)
Fiscal Year 2020: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000)
Fiscal Year 2019: ¥5,720,000 (Direct Cost: ¥4,400,000、Indirect Cost: ¥1,320,000)
Fiscal Year 2018: ¥6,500,000 (Direct Cost: ¥5,000,000、Indirect Cost: ¥1,500,000)
Keywordsパラジウム / 銅 / 選択的合成 / アルキン / 有機ホウ素 / パラジウム触媒 / トリエチルホウ素 / 3-ヒドロキシ-4-ペンテン酸 / 炭素ー炭素結合切断 / オキサパラダサイクル / 結合切断 / ニッケル / 二酸化炭素 / Grob型転位反応 / 脱炭酸 / 共役ジエン / β-ヒドロキシペンテン酸 / アルデヒド / 切断反応 / タンデム反応 / メタラサイクル / カップリング / 炭素-炭素結合切断反応 / 炭素-炭素切断 / ジケテン / 炭素骨格構築
Outline of Final Research Achievements

Pd-catalyzed β-carbon elimination of 3-hydroxy-4-pentenoic acid derivatives promoted by triethylborane proceeded to form conjugated dienes via a decarboxylation process. The formed conjugated dienes underwent the Prins reaction with aldehydes in situ to afford conjugated homoallylic alcohols. These sequential transformations enabled conversion of a diastereomeric mixture of 3-hydroxy-4-pentenoic acids, which were readily prepared from the simple crossed aldol reaction of esters and α,β-unsaturated aldehydes, to 3,5-hexadienyl alcohols with high regio- and stereoselectivities in a single manipulation.

Academic Significance and Societal Importance of the Research Achievements

遷移金属触媒反応は,高効率高選択的合成の重要な汎用手段として,数多く報告されている。特に有機ホウ素を用いた有機合成反応は,鈴木-宮浦クロスカップリング反応をはじめ,重要な母体骨格の炭素-炭素結合骨格形成として有用である。本研究では,有機ホウ素による分子活性化を利用した炭素-炭素結合形成や炭素-炭素結合切断反応による新しい分子変換反応の開発を行った。とりわけ,パラジウムや銅触媒と有機ホウ素による相乗効果を活用した多成分連結反応を検討した。入手容易な基質から,新しい活性中間体の形成を伴いつつ,高効率合成反応を達成することに主眼をおいた。生成物は医薬品や農薬等の生物活性物質として利用できる。

Report

(4 results)
  • 2020 Annual Research Report   Final Research Report ( PDF )
  • 2019 Annual Research Report
  • 2018 Annual Research Report
  • Research Products

    (35 results)

All 2021 2020 2019 2018 Other

All Int'l Joint Research (5 results) Journal Article (15 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 15 results,  Open Access: 2 results) Presentation (14 results) (of which Int'l Joint Research: 1 results) Book (1 results)

  • [Int'l Joint Research] フィリップ大学マールブルグ校/ドルトムント工科大/ゲッティンゲン大学(ドイツ)

    • Related Report
      2020 Annual Research Report
  • [Int'l Joint Research] Chemistry Philipps-Universitat Marburg(ドイツ)

    • Related Report
      2019 Annual Research Report
  • [Int'l Joint Research] ドルトムント工科大/マールブルグ大学/ゲッティンゲン大(ドイツ)

    • Related Report
      2018 Annual Research Report
  • [Int'l Joint Research] フロリダ大学/MIT(米国)

    • Related Report
      2018 Annual Research Report
  • [Int'l Joint Research] オーストラリア国立大学(オーストラリア)

    • Related Report
      2018 Annual Research Report
  • [Journal Article] Hydride Affinities for Main-Group Hydride Reductants: Assessment of Density Functionals and Trends in Reactivities2021

    • Author(s)
      B. Chan, Y. Luo, M. Kimura
    • Journal Title

      Journal of Physical Chemistry A

      Volume: 125 Issue: 3 Pages: 835-842

    • DOI

      10.1021/acs.jpca.0c10543

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ni-Catalyzed Direct Carboxylation of Propargylic Alcohols with Carbon Dioxide2021

    • Author(s)
      Yamahira Tatsuya、Onodera Gen、Fukuda Tsutomu、Kimura Masanari
    • Journal Title

      Chemistry Letters

      Volume: - Issue: 5 Pages: 853-855

    • DOI

      10.1246/cl.210008

    • NAID

      130008040425

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Nickel-Catalyzed Carboxylation of Conjugated Dienes with Carbon Dioxide and DIBAL-H for the Synthesis of β,γ-Unsaturated Carboxylic Acids2020

    • Author(s)
      Kimura Masanari、Luo Ying、Chan Bun、Fukuda Tsutomu、Onodera Gen
    • Journal Title

      Synlett

      Volume: - Issue: 15 Pages: 1551-1554

    • DOI

      10.1055/a-1336-8034

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Direct Benzylation of Amines with Benzylic Alcohols Catalyzed by Palladium/Phosphine-Borane Catalyst System2020

    • Author(s)
      Gen Onodera, Hidenobu Kumagae, Daiki Nakamura, Takuto Hayasaki, Tsutomu Fukuda, Masanari Kimura
    • Journal Title

      Tetrahedron Letters

      Volume: 61 Issue: 47 Pages: 152537-152540

    • DOI

      10.1016/j.tetlet.2020.152537

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Oxidative Hydroxylation of Aryl Boronic acid Catalyzed by Co-porphyrin Complexes via Blue-Light Irradiation2020

    • Author(s)
      A. A. Atia, M. Kimura
    • Journal Title

      Catalysts

      Volume: 10 Issue: 11 Pages: 1-10

    • DOI

      10.3390/catal10111262

    • NAID

      120006988467

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Enantioselective Ring-Closing C?H Amination of Urea Derivatives2020

    • Author(s)
      Zhou Zijun、Tan Yuqi、Yamahira Tatsuya、Ivlev Sergei、Xie Xiulan、Riedel Radostan、Hemming Marcel、Kimura Masanari、Meggers Eric
    • Journal Title

      Chem

      Volume: 6 Issue: 8 Pages: 2024-2034

    • DOI

      10.1016/j.chempr.2020.05.017

    • Related Report
      2020 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Pd-Catalyzed Dehydrogenative Oxidation of Alcohols to Functionalized Molecules2019

    • Author(s)
      Mori, T.; Ishii, C.; Kimura, M
    • Journal Title

      Organic Process Research and Development

      Volume: 23 Issue: 8 Pages: 1709-1717

    • DOI

      10.1021/acs.oprd.9b00207

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Assessment of DFT Methods for Transition Metals with the TMC151 Compilation of Data Sets and Comparison with Accuracies for Main-Group Chemistry2019

    • Author(s)
      Chan, B.; Gill, P. M. W.; Kimura, M.
    • Journal Title

      Journal of Chemical Theory and Computation

      Volume: 15 Issue: 6 Pages: 3610-3622

    • DOI

      10.1021/acs.jctc.9b00239

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis and Evaluation of Topoisomerase I Inhibitors Possessing the 5,13-Dihydro-6H-benzo[6,7]indolo[3,2-c]quinolin-6-one Scaffold2019

    • Author(s)
      Fukuda Tsutomu、Matsuoka Fuyuki、Matsuo Yuri、Yoshioka Naoki、Onodera Gen、Kimura Masanari、Ishibashi Fumito、Iwao Masatomo
    • Journal Title

      HETEROCYCLES

      Volume: 99 Issue: 2 Pages: 1032-1032

    • DOI

      10.3987/com-18-s(f)70

    • NAID

      120006988387

    • Related Report
      2019 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Mechanism for Three-Component Ni-Catalyzed Carbonyl-Ene Reaction for CO2 Transformation: What Practical Lessons Do We Learn from DFT Modelling?2019

    • Author(s)
      B. Chan, Y. Luo, M. Kimura
    • Journal Title

      Aust. J. Chem.

      Volume: 71 Issue: 4 Pages: 272-278

    • DOI

      10.1071/ch17573

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ni-Catalyzed Reconstruction of Carbon Frameworks via C-C Bond Cleavage Reactions2018

    • Author(s)
      木村正成
    • Journal Title

      Journal of Synthetic Organic Chemistry, Japan

      Volume: 76 Issue: 12 Pages: 1324-1331

    • DOI

      10.5059/yukigoseikyokaishi.76.1324

    • NAID

      130007529569

    • ISSN
      0037-9980, 1883-6526
    • Year and Date
      2018-12-01
    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ni-Catalyzed Formal Carbonyl-Ene Reaction of Terminal Alkenes via Carbon Dioxide Insertion2018

    • Author(s)
      Yasuyuki Mori, Chieko Shigeno, Ying Luo, Bun Chan, Gen Onodera, Masanari Kimura
    • Journal Title

      Synlett

      Volume: 29 Issue: 06 Pages: 742-746

    • DOI

      10.1055/s-0036-1591845

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Synthesis of 4,5-Disubstituted Pyrano[3,4-b]Pyrrol-7(1H)- Ones via Sonogashira?Hagihara Cross-Coupling of N-Benzenesulfonyl-3-bromo-1H-pyrrole-2-carboxylate and Subsequent Iodine-mediated Cyclization2018

    • Author(s)
      Fukuda Tsutomu、Komure Minoru、Onodera Gen、Kimura Masanari、Iwao Masatomo
    • Journal Title

      HETEROCYCLES

      Volume: 97 Issue: 2 Pages: 916-930

    • DOI

      10.3987/com-18-s(t)68

    • NAID

      120006987766

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Recent topics in the syntheses of β-keto carboxylic acids and the derivatives2018

    • Author(s)
      Masanari Kimura
    • Journal Title

      Tetrahedron Lett.

      Volume: 59 Issue: 14 Pages: 1295-1300

    • DOI

      10.1016/j.tetlet.2018.02.049

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Direct Allylation of Active Methylene Compounds with Allylic Alcohols by Use of Palladium/Phosphine-Borane Catalyst System2018

    • Author(s)
      Aika Shimizu, Goki Hirata, Gen Onodera, Masanari Kimura
    • Journal Title

      Advanced Synthesis & Catalysis

      Volume: 印刷中 Issue: 10 Pages: 1954-1960

    • DOI

      10.1002/adsc.201800187

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Presentation] ニッケル触媒を用いた二酸化炭素によるプロパルギルアルコールの直接的カルボキシル化反応2021

    • Author(s)
      山平 達也、福田 勉、小野寺 玄、木村 正成
    • Organizer
      日本化学会 第101春季年会(2021)
    • Related Report
      2020 Annual Research Report
  • [Presentation] アザラメラリンDおよびNの全合成2021

    • Author(s)
      角 真由、奥谷 浄也、宮城 一仁、福田 勉、小野寺 玄、木村 正成
    • Organizer
      日本化学会 第101春季年会(2021)
    • Related Report
      2020 Annual Research Report
  • [Presentation] 金/ホスフィン-ボラン触媒系によるアルキン部位を有するマロン酸エステル誘導体のConia-Ene反応2021

    • Author(s)
      桑原 麟太郎、小野寺  玄、福田 勉、Norbert Krause、木村 正成
    • Organizer
      日本化学会 第101春季年会(2021)
    • Related Report
      2020 Annual Research Report
  • [Presentation] 多置換アルケンの高選択的合成を志向したオキサボロールの新規合成反応の開発2020

    • Author(s)
      末吉巽,布田旭,阿嘉由樹,福田勉,小野寺玄,木村正成
    • Organizer
      日本化学会第100春季年会
    • Related Report
      2019 Annual Research Report
  • [Presentation] パラジウム触媒とホスフィン―ボラン配位子を用いたアルデヒドのα位アリル化反応2019

    • Author(s)
      早﨑匠杜,小野寺玄,福田勉,木村正成
    • Organizer
      第56回化学関連支部合同九州大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] ホスフィン―ボラン配位子と金触媒を用いたアルキン部位を有するマロン酸エステル誘導体のConia-Ene反応2019

    • Author(s)
      桑原麟太郎,小野寺玄,福田勉,Norbert Krause,木村正成
    • Organizer
      第56回化学関連支部合同九州大会
    • Related Report
      2019 Annual Research Report
  • [Presentation] 銅触媒による末端アルキンと有機ホウ素及びアルデヒドを用いたオキサボロールの新規合成反応の開発2019

    • Author(s)
      布田旭,阿嘉由樹,福田勉,小野寺玄,木村正成
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] ホスフィン―ボラン配位子を用いたアリルアルコールによるカルボニル化合物のα位アリル化反応2019

    • Author(s)
      戸上翔太郎,早﨑匠杜,清水愛香,福田勉,小野寺玄,木村正成
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] パラジウム触媒とトリエチルホウ素を用いた3-ヒドロキシ-4-ペンテン酸とアルデヒドとのカップリング反応2019

    • Author(s)
      仲尾純弥,神路祗里歩,福田勉,小野寺玄,木村正成
    • Organizer
      第66回有機金属化学討論会
    • Related Report
      2019 Annual Research Report
  • [Presentation] パラジウム触媒作用による3-ヒドロキシ-4-ペンテン酸を共役ジエン等価体として活用したアルデヒドとのカップリング反応2019

    • Author(s)
      仲尾純弥, ニノ方亮, 神路祗里歩, 福田勉, 小野寺玄, 木村正成
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 末端アルキンと有機ホウ素及びアルデヒドを用いたアルキニルボレートを介するオキサボロールの新規合成法の開発2019

    • Author(s)
      布田旭, 藤田勇輝, 阿嘉由樹, 福田勉, 小野寺玄, 木村正成
    • Organizer
      日本化学会 第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] オキサボロールを介したα,β-不飽和エノンの新規合成法の開発2018

    • Author(s)
      藤田勇輝, 阿嘉由樹, 布田旭, 福田勉, 小野寺玄, 木村正成
    • Organizer
      第48回複素環化学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Cu-Catalyzed Stereoselective Formation of a,b-Unsaturated Carbonyls via Alkynylborates2018

    • Author(s)
      Masanari Kimura
    • Organizer
      IKCOC-14
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Ni触媒作用による二酸化炭素を用いたテルペノイドのヒドロカルボキシル反応2018

    • Author(s)
      Luo Ying, 小野寺玄, 福田勉, 木村正成
    • Organizer
      第62回香料・テルペンおよび精油化学に関する討論会
    • Related Report
      2018 Annual Research Report
  • [Book] “Carbonyl-Ene Reactions of Alkenes with Carbon Dioxide”, In CO2 as a Building Block in Organic Synthesis, Edited by S. Das2020

    • Author(s)
      Y. Mori, M. Kimura
    • Publisher
      WILEY-VCH
    • ISBN
      9783527346134
    • Related Report
      2020 Annual Research Report

URL: 

Published: 2018-04-23   Modified: 2022-01-27  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi