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Direct functionalization of aliphatic alcohols by transition metal catalysis

Research Project

Project/Area Number 24550122
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Synthetic chemistry
Research InstitutionOsaka Prefecture University

Principal Investigator

FUKUYAMA Takahide  大阪府立大学, 理学(系)研究科(研究院), 准教授 (60332962)

Project Period (FY) 2012-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥5,330,000 (Direct Cost: ¥4,100,000、Indirect Cost: ¥1,230,000)
Fiscal Year 2014: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2013: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
Fiscal Year 2012: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
Keywordsアルコール / 直接官能基化 / ケトン / アミド / ニトリル / ルテニウムヒドリド / 水素移動反応 / 異性化 / アルケン / ホモアリルカーボネート / アリル位アルキル化 / 水素移動型反応 / α位アルキル化 / アセトアミド / 窒素系配位子
Outline of Final Research Achievements

Direct functionalization of aliphatic alcohols was investingated. α-Alkylation of carbonyl compounds, such as ketones, amides, and acetonitrile, using primary aliphatic alcohols was effectively catalyzed by RuHCl(CO)(PPh3)3. The present reaction would proceed via RuH-catalyzed transfer dehydrogenation of alcohols to aldehydes, which then undergo base promoted aldol condensation with carbonyl compounds to give α,β-unsaturated compounds. Finally transfer hydrogenation of thus formed α,β-unsaturated compounds with alcohols would provide the α-alkylated products. RuHCl(CO)(PPh3)3 was also found to be effective for selective olefin isomerization of protected homoallyl alcohols.  The reaction of homoallyl carbonate with malonic acid esters gave coupling product via sequential olefin isomerization and allylic alkylation reaction.

Report

(4 results)
  • 2014 Annual Research Report   Final Research Report ( PDF )
  • 2013 Research-status Report
  • 2012 Research-status Report
  • Research Products

    (22 results)

All 2015 2014 2013 2012

All Journal Article (4 results) (of which Peer Reviewed: 4 results,  Open Access: 1 results,  Acknowledgement Compliant: 1 results) Presentation (18 results) (of which Invited: 2 results)

  • [Journal Article] Synthesis of Fluorenones through Rhodium-Catalyzed Intramolecular Acylation of Biarylcarboxylic Acids2014

    • Author(s)
      Fukuyama, T.; Maetani, S.; Miyagawa, K.; Ryu, I.
    • Journal Title

      Organic Letters

      Volume: 16 Issue: 12 Pages: 3216-3219

    • DOI

      10.1021/ol5012407

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Synthesis of Alkylated Nitriles by [RuHCl(CO)(PPh3)3]-catalyzed Alkylation of Acetonitrile Using Primary Alcohols2013

    • Author(s)
      Kuwahara, T.; Fukuyama, T.; Ryu, I.
    • Journal Title

      Chem. Lett.

      Volume: 42 Issue: 10 Pages: 1163-1165

    • DOI

      10.1246/cl.130465

    • NAID

      10031201296

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Ruthenium hydride/nitrogen tridentate ligand-catalyzed alpha-alkylation of acetamides with primary alcohols2013

    • Author(s)
      Kuwahara, T.; Fukuyama, T.; Ryu, I.
    • Journal Title

      RSC Adv.

      Volume: 3 Issue: 33 Pages: 13702-13704

    • DOI

      10.1039/c3ra42834f

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] RuHCl(CO)(PPh3)3-Catalyzed α-Alkylation of Ketones with Primary Alcohols2012

    • Author(s)
      Kuwahara, T.; Fukuyama, T.; Ryu, I.
    • Journal Title

      Org. Lett.

      Volume: 14 Issue: 18 Pages: 4703-4705

    • DOI

      10.1021/ol302145a

    • Related Report
      2012 Research-status Report
    • Peer Reviewed
  • [Presentation] ルテニウムヒドリド触媒を用いたホモアリルシリルエーテルの異性化反応2015

    • Author(s)
      桒原 崇、山本悠暉、福山高英、柳 日馨
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      船橋、日本大学
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] 遷移金属触媒によるアルケニルエステル類のオレフィン異性化反応2015

    • Author(s)
      桒原 崇、福山高英、柳 日馨
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      船橋、日本大学
    • Year and Date
      2015-03-26 – 2015-03-29
    • Related Report
      2014 Annual Research Report
  • [Presentation] Synthesis of Polycyclic Compounds through Rhodium-Catalyzed Cyclization of Aromatic Carboxylic Acids2014

    • Author(s)
      Fukuyama, T.
    • Organizer
      8th Singapore International Chemsitry Conference
    • Place of Presentation
      Singapore, Royton Sapporo
    • Year and Date
      2014-12-14 – 2014-12-17
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Selective Olefin Isomerization of Homoallyl Silyl Ethers to Allyl Silyl Ethers Catalyzed by Ruthenium Hydride Complex2014

    • Author(s)
      Kuwahara, T.; Yamamoto, Y.; Fukuyama, T.; Ryu, I.
    • Organizer
      The 9th International Symposium on Integrated Synthesis
    • Place of Presentation
      Hyogo, Awaji Yumebutai International Conference Center
    • Year and Date
      2014-11-14 – 2014-11-15
    • Related Report
      2014 Annual Research Report
  • [Presentation] Synthesis of Fluorenones through Rhodium-Catalyzed Intramolecular Acylation of Biarylcarboxylic Acids2014

    • Author(s)
      Fukuyama, T.; Maetani, S.; Miyagawa, K.; Ryu, I.
    • Organizer
      XXIV International Conferrence on Organometallic Chemistry
    • Place of Presentation
      Sapporo, Royton Sapporo
    • Year and Date
      2014-07-13 – 2014-07-18
    • Related Report
      2014 Annual Research Report
  • [Presentation] ルテニウムヒドリド触媒によるオレフィン異性化とアリル位アルキル化による新規C-C結合形成反応2014

    • Author(s)
      桒原 崇・福山高英・柳 日馨
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      愛知県
    • Related Report
      2013 Research-status Report
  • [Presentation] Alkylation of Acetonitrile and Acetamides Using Primary Alcohols Catalyzed by Ruthenium Hydride/Tridentate Nitrogen Ligand System2013

    • Author(s)
      Takashi Kuwahara, Takahide Fukuyama, and Ilhyong Ryu
    • Organizer
      0th International Symposium on Carbanion Chemistry
    • Place of Presentation
      Kyoto
    • Related Report
      2013 Research-status Report
  • [Presentation] RuHCl(CO)(PPh3)3-Catalyzed α-Alkylation of Acetonitrile and Acetamides Using Primary Alcohols2013

    • Author(s)
      Takashi Kuwahara, Takahide Fukuyama, and Ilhyong Ryu
    • Organizer
      60th Symposium on Organometallic Chemistry, Japan
    • Place of Presentation
      Tokyo
    • Related Report
      2013 Research-status Report
  • [Presentation] RuHCl(CO)(PPh3)3-Catalyzed Alkylation of Acetamides Using Primary Alcohols2013

    • Author(s)
      Takashi Kuwahara, Takahide Fukuyama, and Ilhyong Ryu
    • Organizer
      International Symposium on Relations between Homogeneous and Heterogeneous Catalysis
    • Place of Presentation
      Sapporo
    • Related Report
      2013 Research-status Report
  • [Presentation] ルテニウム触媒による第1級アルコールを用いたアセトアミド類のα-アルキル化反応2013

    • Author(s)
      桒原崇・福山高英・柳 日馨
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      滋賀
    • Related Report
      2012 Research-status Report
  • [Presentation] ルテニウム触媒による1,3-ジケトン類の末端アルキンへの位置選択的付加反応2013

    • Author(s)
      レオタルド ベンジャミン・福山高英・セリア ブランクール・岡本裕美・柳 日馨
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      滋賀
    • Related Report
      2012 Research-status Report
  • [Presentation] ロジウム触媒を用いる2-アリロキシ安息香酸の脱カルボニル的環化反応によるジベンゾフラン類の合成2013

    • Author(s)
      前谷臣治・福山高英・柳 日馨
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      滋賀
    • Related Report
      2012 Research-status Report
  • [Presentation] ロジウム触媒を用いるビアリールカルボン酸の分子内アシル化によるフルオレノン類の合成2013

    • Author(s)
      前谷臣治・宮川和紗・福山高英・柳 日馨
    • Organizer
      日本化学会第93春季年会
    • Place of Presentation
      滋賀
    • Related Report
      2012 Research-status Report
  • [Presentation] フローマイクロリアクターを用いた均一系触媒反応2013

    • Author(s)
      福山高英
    • Organizer
      フロー・マイクロ合成研究会 第57回研究会
    • Place of Presentation
      福井
    • Related Report
      2012 Research-status Report
    • Invited
  • [Presentation] ルテニウムヒドリド錯体を触媒とする第1級アルコールを用いたケトンのα-アルキル化反応2012

    • Author(s)
      桒原 崇・福山高英・柳 日馨
    • Organizer
      第39回有機反応懇談会
    • Place of Presentation
      大阪
    • Related Report
      2012 Research-status Report
  • [Presentation] Rhodium-Catalyzed Decarbonylative Cyclization of 2-Aryloxybenzoic Acids Leading to Dibenzofurans2012

    • Author(s)
      Shinji Metani, Takahide Fukuyama, and Ilhyong Ryu
    • Organizer
      The 12th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-12)
    • Place of Presentation
      Kyoto
    • Related Report
      2012 Research-status Report
  • [Presentation] Rhodium-Catalyzed Synthesis of Dibenzofurans via Decarbonylative Cyclization of 2-Phenoxybenzoic Acids and their Esters2012

    • Author(s)
      Shinji Metani, Takahide Fukuyama, and Ilhyong Ryu
    • Organizer
      59th Symposium on Organometallic Chemistry
    • Place of Presentation
      Osaka
    • Related Report
      2012 Research-status Report
  • [Presentation] Effective Alkylation of Ketones with Primary Alcohols Catalyzed by Ruthenium Hydride2012

    • Author(s)
      Takashi Kuwahara, Takahide Fukuyama, and Ilhyong Ryu
    • Organizer
      59th Symposium on Organometallic Chemistry
    • Place of Presentation
      Osaka
    • Related Report
      2012 Research-status Report

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Published: 2013-05-31   Modified: 2019-07-29  

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