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Reconstruction of Molecular Framework by C-C Bond Formation and Cleavage via Metalacycles

Research Project

Project/Area Number 26288052
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypePartial Multi-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionNagasaki University

Principal Investigator

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

Co-Investigator(Kenkyū-buntansha) 重光 保博  長崎大学, 工学研究科, 准教授 (50432969)
小野寺 玄  長崎大学, 工学研究科, 助教 (90433698)
Project Period (FY) 2014-04-01 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥16,640,000 (Direct Cost: ¥12,800,000、Indirect Cost: ¥3,840,000)
Fiscal Year 2016: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000)
Fiscal Year 2015: ¥5,330,000 (Direct Cost: ¥4,100,000、Indirect Cost: ¥1,230,000)
Fiscal Year 2014: ¥6,630,000 (Direct Cost: ¥5,100,000、Indirect Cost: ¥1,530,000)
Keywordsニッケル / 銅 / 有機アルミニウム / 有機亜鉛 / アルキン / 二酸化炭素 / 共役ジエン / カーボネート / ジケテン / 多成分連結 / 炭素-炭素結合切断 / 合成化学 / 切断反応 / カップリング / 高効率 / フェニル酢酸
Outline of Final Research Achievements

Although cyclic carbonates are utilized in fine chemicals and as monomers for polymerization in modern industrial synthesis, most synthetic utilities of 1,3-dioxolan-2-ones face difficulties due to the decarboxylation reaction. In this study, we have developed 4-methylene-1,3-dioxolan-2-one undergoes oxidative addition of Ni(0) catalyst in the presence of Me2Al(OMe) followed by a coupling reaction with alkynes to form unsaturated beta-ketocarboxylic acids with high regio- and stereoselectivities.
As an alternative development for CO2 fixation processes, we envisaged the three-component coupling reaction of terminal alkyne, trialkylboranes, and CO2 to yield alpha-substituted acrylic acids as a single product. Cu-catalyzed CO2 insertion reactions involving a dialkylvinylborane intermediate derived from alkynyltrialkylborate by a 1,2-alkyl group migration were carried out to afford α-alkylated acrylic acids with excellent regio- and stereoselectivities.

Report

(4 results)
  • 2016 Annual Research Report   Final Research Report ( PDF )
  • 2015 Annual Research Report
  • 2014 Annual Research Report
  • Research Products

    (31 results)

All 2017 2016 2015 2014 Other

All Int'l Joint Research (2 results) Journal Article (12 results) (of which Peer Reviewed: 12 results,  Acknowledgement Compliant: 10 results,  Open Access: 1 results) Presentation (11 results) (of which Invited: 5 results) Book (5 results) Remarks (1 results)

  • [Int'l Joint Research] ドルトムント工科大学(ドイツ)

    • Related Report
      2015 Annual Research Report
  • [Int'l Joint Research] ゲッティンゲン大学(ドイツ)

    • Related Report
      2015 Annual Research Report
  • [Journal Article] Copper-Catalyzed Stereodefined Construction of Acrylic Acid Derivatives from Terminal Alkynes via CO2 Insertion2017

    • Author(s)
      K. Kuge, Y. Luo, Y. Fujita, Y. Mori, G. Onodera, M. Kimura
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 4 Pages: 854-857

    • DOI

      10.1021/acs.orglett.6b03860

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Ni-Catalyzed CO2 Rearrangement of Enolative Metal Carbonate for Efficient Synthesis of β-Ketocarboxylic Acid2017

    • Author(s)
      R. Ninokata, T. Yamahira, G. Onodera, *M. Kimura
    • Journal Title

      Angew. Chem. Int Ed.

      Volume: 56 Issue: 1 Pages: 208-211

    • DOI

      10.1002/anie.201609338

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Ni-Catalyzed Three-component Coupling of 4-Methylene-2-oxazolidinones, Alkynes, and Trimethylaluminum2017

    • Author(s)
      T. Yamahira, R. Ninokata, G. Onodera, M. Kimura
    • Journal Title

      Heterocycles

      Volume: 95 Issue: 2 Pages: 722-722

    • DOI

      10.3987/com-16-s(s)59

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Remarkably Selective Formation of Allenyl and Dienyl Alcohols via Ni-Catalyzed Coupling Reaction of Conjugated Enyne, Aldehyde, and Organozinc Reagents2016

    • Author(s)
      Y. Mori, T. Kawabata, G. Onodera, M. Kimura
    • Journal Title

      Synthesis

      Volume: 48 Issue: 15 Pages: 2385-2395

    • DOI

      10.1055/s-0035-1560448

    • Related Report
      2016 Annual Research Report 2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis and X-ray Crystal Structure of Novel Cobalt(II) Complexes Having Oligopyridine Ligands2016

    • Author(s)
      G. Onodera, G. Hirata, T. Seike, R. Takeuchi, M. Kimura
    • Journal Title

      Polyhedron

      Volume: 112 Pages: 43-50

    • DOI

      10.1016/j.poly.2016.03.029

    • Related Report
      2016 Annual Research Report 2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Efficient Synthesis of Pyrrolizidine by Pd-Catalyzed Consecutive Double Amphiphilic Allylation of Nitrile2015

    • Author(s)
      Yamada, N.; Hirata, G.; Onodera, G.; Kimura, M
    • Journal Title

      Tetrahedron

      Volume: 71 Issue: 37 Pages: 6541-6546

    • DOI

      10.1016/j.tet.2015.04.110

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed
  • [Journal Article] “Palladium-Catalyzed [4+2] Cycloaddition of Aldimines and 1,4-Dipolar Equivalents via Amphiphilic Allylation”2015

    • Author(s)
      G. Hirata, N. Yamada, S. Sanada, G. Onodera, M. Kimura
    • Journal Title

      Org. Lett.

      Volume: 17 Issue: 3 Pages: 600-603

    • DOI

      10.1021/ol503614d

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Three-Component Coupling Reaction of Enynes, Carbonyls, and Organozinc Reagents2015

    • Author(s)
      Y. Ohira, T. Mori, M. Hayashi, G. Onodera, M. Kimura
    • Journal Title

      Heterocycles

      Volume: 90 Issue: 2 Pages: 832-841

    • DOI

      10.3987/com-14-s(k)65

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] “Synthesis of Lactones and Lactams from Vinylcyclopropane by Pd-Catalyzed Nucleophilic Allylation”2014

    • Author(s)
      G. Hirata, G. Onodera, M. Kimura
    • Journal Title

      Synlett

      Volume: 25 Issue: 16 Pages: 2306-2310

    • DOI

      10.1055/s-0034-1378566

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Ni-Catalyzed Multi-component Coupling Reaction of Alkyne, 1,3-Butadiene, and Me_2Zn under Carbon Dioxade2014

    • Author(s)
      Y. Mori, T. Mori, G. Onodera, M. Kimura
    • Journal Title

      Synthesis

      Volume: (印刷中)(掲載確定) Issue: 17 Pages: 2287-2292

    • DOI

      10.1055/s-0033-1339024

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Efficient and Selective Formation of Unsaturated Carboxylic Acids and Phenylacetic Acids from Diketene2014

    • Author(s)
      T. Mori, Y. Akioka, H. Kawahara, R. Ninokata, G. Onodera, M. Kimura
    • Journal Title

      Angew. Chem. Int. Ed.

      Volume: 53 Issue: 39 Pages: 10434-10438

    • DOI

      10.1002/anie.201404816

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Ni-Catalyzed Homoallylation of Polyhydroxy N,O-Acetals with Conjugated Dienes Promoted by Triethylborane2014

    • Author(s)
      T. Mori, Y. Akioka, G. Onodera, M. Kimura
    • Journal Title

      Molecules

      Volume: 19 Issue: 7 Pages: 9288-9306

    • DOI

      10.3390/molecules19079288

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Presentation] Highly Stereoselective Synthesis of Acrylic Acid Derivatives via Three Component Coupling of Terminal Alkyne, Organoborane, and Carbon Dioxide2016

    • Author(s)
      K.Kuge, Y. Mori, G. Onodera, M. Kimura
    • Organizer
      63rd Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      東京都・新宿区・早稲田大学
    • Year and Date
      2016-09-14
    • Related Report
      2016 Annual Research Report
  • [Presentation] Synthesis of beta-Keto Acid via Transformation of Cyclic Carbonate Using Nickel Catalyst and Organoaluminum Reagent2016

    • Author(s)
      R. Ninokata, G. Onodera, M. Kimura
    • Organizer
      63rd Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      東京都・新宿区・早稲田大学
    • Year and Date
      2016-09-14
    • Related Report
      2016 Annual Research Report
  • [Presentation] Direct Allylic Alkylation of Allic Alcohols Catalyzed by Palladium and Phosphine-Borane Ligand2016

    • Author(s)
      A. Shimizu, G. Hirata, G. Onodera, M. Kimura
    • Organizer
      63rd Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      東京都・新宿区・早稲田大学
    • Year and Date
      2016-09-14
    • Related Report
      2016 Annual Research Report
  • [Presentation] 銅触媒を用いた有機ホウ素と末端アルキン及び二酸化炭素の位置及び立体選択的三成分連結反応2016

    • Author(s)
      久家健太、森 康友紀、小野寺玄、木村正成
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大(京都府・京田辺市多々羅都谷)
    • Year and Date
      2016-03-23
    • Related Report
      2015 Annual Research Report
  • [Presentation] Pd触媒による第1級アルコールとアニリン誘導体との反応による含窒素複素環化合物の新規合成法2015

    • Author(s)
      石井千尋、米倉篤志、森 崇理、小野寺玄、木村正成
    • Organizer
      第45回複素環化学討論会
    • Place of Presentation
      早稲田大学(東京都・新宿区西早稲田)
    • Year and Date
      2015-11-19
    • Related Report
      2015 Annual Research Report
  • [Presentation] パラジウム触媒とホスフィン-ボラン配位子によるアリルアルコールの直接的アリル位置換反応2015

    • Author(s)
      小野寺玄、平田剛輝、里村秀昭、木村正成
    • Organizer
      第62回有機金属化学討論会
    • Place of Presentation
      関西大学(大阪府・吹田市山手町)
    • Year and Date
      2015-09-07
    • Related Report
      2015 Annual Research Report
  • [Presentation] パラジウム触媒と有機ホウ素の相乗効果を利用した炭素-炭素結合形成反応2015

    • Author(s)
      木村正成
    • Organizer
      第48回有機金属若手の会 夏の学校
    • Place of Presentation
      白浜荘(滋賀県・高島市安曇川町)
    • Year and Date
      2015-07-13
    • Related Report
      2015 Annual Research Report
    • Invited
  • [Presentation] 双極的アリル化反応を活用した有用物質創製2015

    • Author(s)
      木村正成
    • Organizer
      第39回有機電子移動化学討論会
    • Place of Presentation
      長崎大学(長崎県・長崎市文教町)
    • Year and Date
      2015-06-25
    • Related Report
      2015 Annual Research Report
    • Invited
  • [Presentation] Efficient Formation of Unsaturated Carboxylic Acids and Phenylacetic Acids from Diketene via Nickelacycles2014

    • Author(s)
      M. Kimura
    • Organizer
      18th Malaysian International Chemical Congress
    • Place of Presentation
      Kuala Lumpur, Malaysia(Putra World Trade Center)
    • Year and Date
      2014-11-02 – 2014-11-04
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Selective formation of unsaturated carboxylic acids and phenylacetic acids from diketene2014

    • Author(s)
      ○M. Kimura, T. Mori, G. Onodera
    • Organizer
      15th Tetrahedron Symposium - Asian Edition
    • Place of Presentation
      singapore(EXSPO)
    • Year and Date
      2014-10-28 – 2014-10-30
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Efficient Formation of Unsaturated Carboxylic Acids and Phenylacetic Acids from Diketene via Nickelacycles2014

    • Author(s)
      木村正成
    • Organizer
      XXVI International Conference on Organometallic Chemistry (ICOMC2014)
    • Place of Presentation
      札幌市(ロイトンホテル)
    • Year and Date
      2014-07-15 – 2014-07-18
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Book] 二酸化炭素を用いた化学品製造技術2016

    • Author(s)
      杉本裕、木村正成(共著)
    • Total Pages
      300
    • Publisher
      S&T出版
    • Related Report
      2016 Annual Research Report
  • [Book] 「二酸化炭素を用いた化学品製造技術」2016

    • Author(s)
      杉本裕 監修、木村正成他
    • Total Pages
      305
    • Publisher
      S&T出版株式会社
    • Related Report
      2015 Annual Research Report
  • [Book] 「二酸化炭素を使いこなす!炭素資源としての有効活用」,最新のトピックス,化学2015

    • Author(s)
      木村正成
    • Total Pages
      76
    • Publisher
      化学同人
    • Related Report
      2015 Annual Research Report
  • [Book] 有機合成実験法ハンドブック 第2版  19. 有機金属化合物を用いる合成反応実験法2015

    • Author(s)
      有機合成化学協会 編 中井 武 監修、木村正成他
    • Total Pages
      1202
    • Publisher
      丸善出版
    • Related Report
      2015 Annual Research Report
  • [Book] Comprehensive Organic Synthesis II2014

    • Author(s)
      Comprehensive Organic Synthesis II
    • Total Pages
      19
    • Publisher
      Elsevire
    • Related Report
      2014 Annual Research Report
  • [Remarks] 長崎大学大学院化学・物質工学コース 生物有機化学研究室

    • URL

      http://www.cms.nagasaki-u.ac.jp/lab/yuuki/

    • Related Report
      2014 Annual Research Report

URL: 

Published: 2014-04-04   Modified: 2018-03-22  

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