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

細孔内を反応場とする脱カルボキシル化/カルボキシル化を伴う新反応開発

Publicly Offered Research

Project AreaPrecise Formation of a Catalyst Having a Specified Field for Use in Extremely Difficult Substrate Conversion Reactions
Project/Area Number 16H01037
Research Category

Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionOsaka City University

Principal Investigator

佐藤 哲也  大阪市立大学, 大学院理学研究科, 教授 (40273586)

Project Period (FY) 2016-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000)
Fiscal Year 2017: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Fiscal Year 2016: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
Keywordsカルボン酸 / ロジウム触媒 / 酸化的カップリング / 炭素―水素結合切断 / 有機化学 / 炭素ー水素結合切断 / クロスカップリング / 炭素ー炭素結合形成
Outline of Annual Research Achievements

カルボン酸類は、化学的に安定で取り扱いやすく、また化石資源だけでなくバイオマスを始めとする多様な有機資源から得られるため、有機合成における重要なビルディングブロックとなっている。カルボキシル基は遷移金属触媒の金属中心に適度に配位するため、配向基として機能し、近傍の炭素―水素結合を直接誘導体化することが可能となる。例えば我々は、ペンタメチルシクロペンタジエニルロジウム触媒および銀塩を酸化剤として用い、アクリル酸類をアルケンやアルキンとともに反応させると、カルボキシル基のロジウム中心への配位を鍵としてβ位の炭素―水素結合が切断され、酸化的カップリング生成物を与えることを報告している。
本研究の2年目にあたる平成29年度には、これら同じ組み合わせの基質を、ロジウム触媒を添加せずに銀塩のみを用いて反応させると、アルキンの三重結合へのカルボキシル基の付加が立体選択的に起こり、(Z)-エノールエステルが得られることを見出した。脂肪族カルボン酸の反応では、触媒量の銀塩存在下でもスムーズに進行した。
またカルボキシル基を配向基として利用した炭素―水素結合の直接誘導体化についても引き続き検討し、ロジウム触媒を用いる条件では、N-フェニルインドール-3-カルボン酸とアルケンおよびアルキンとの酸化的カップリングが効率よく進行し、拡張されたπ共役系を有するインドール誘導体を合成できることを明らかにした。さらにカルボン酸類と同様に入手容易なサリチルアルデヒドとアルキンとの新規酸化的カップリングを開発することにも成功した。

Research Progress Status

29年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

29年度が最終年度であるため、記入しない。

Report

(2 results)
  • 2017 Annual Research Report
  • 2016 Annual Research Report
  • Research Products

    (29 results)

All 2018 2017 2016

All Journal Article (9 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 9 results,  Open Access: 1 results,  Acknowledgement Compliant: 4 results) Presentation (17 results) (of which Int'l Joint Research: 11 results,  Invited: 10 results) Book (3 results)

  • [Journal Article] Synthesis of Enol Esters through Silver-catalyzed or -mediated Hydroacyloxylation of Internal Alkynes2018

    • Author(s)
      Kikui, N.; Hinoue, T.; Usuki, Y.; Satoh, T.
    • Journal Title

      Chem. Lett.

      Volume: 47 Issue: 2 Pages: 141-143

    • DOI

      10.1246/cl.170986

    • NAID

      130006337757

    • URL

      https://ocu-omu.repo.nii.ac.jp/records/2019742

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Iridium‐Catalyzed Aerobic Coupling of Salicylaldehydes with Alkynes: A Remarkable Switch of Oxacyclic Product2018

    • Author(s)
      Shintaro Yamane, Tomoaki Hinoue, Yoshinosuke Usuki, Masumi Itazaki, Hiroshi Nakazawa, Yoshihiro Hayashi, Susumu Kawauchi, Masahiro Miura, Tetsuya Satoh
    • Journal Title

      Chemistry - An Europian Journal

      Volume: 24 Issue: 31 Pages: 7852-7855

    • DOI

      10.1002/chem.201801245

    • NAID

      120006649311

    • URL

      https://ocu-omu.repo.nii.ac.jp/records/2019730

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Rhodium(III)-Catalyzed Oxidative Coupling of N-Phenylindole-3-carboxylic Acids with Alkenes and Alkynes via C4H and C2H/C2H Bond Cleavage2018

    • Author(s)
      Okada, T.; Sakai, A.; Hinoue, T.; Satoh, T.; Hayashi, Y.; Kawauchi, S.; Cahndrababunaidu, K.; Miura, M.
    • Journal Title

      J. Org. Chem.

      Volume: 83 Issue: 10 Pages: 5639-5649

    • DOI

      10.1021/acs.joc.8b00638

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Total Syntheses and Configuration Assignments of JBIR-04 and Unantimycin A2017

    • Author(s)
      Usuki, Y.; Hamada, C.; Satoh, T.
    • Journal Title

      Org. Biomol. Chem.

      Volume: 15 Issue: 35 Pages: 7346-7351

    • DOI

      10.1039/c7ob01732d

    • NAID

      120006510937

    • URL

      https://ocu-omu.repo.nii.ac.jp/records/2020129

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Rhodium(III)-Catalyzed Ortho-Alkenylation of Anilines Directed by a Removable Boc-Protecting Group2017

    • Author(s)
      Morita Tomohiro、Satoh Tetsuya、Miura Masahiro
    • Journal Title

      Organic Letters

      Volume: 19 Issue: 7 Pages: 1800-1803

    • DOI

      10.1021/acs.orglett.7b00569

    • Related Report
      2017 Annual Research Report 2016 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Construction of Bisbenzofuro[2,3-b:3',2'-e]pyridines by Palladium-Catalyzed Double Intramolecular Oxidative C-H/C-H Coupling2017

    • Author(s)
      Kaida, H.; Goya, T.; Nishii, Y.; Hirano, K.;. Satoh, T.; Miura, M.
    • Journal Title

      Org. Lett.

      Volume: 19 Issue: 5 Pages: 1236-1239

    • DOI

      10.1021/acs.orglett.7b00323

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Synthesis of Difluorinated Enynes through Sonogashira-Type Coupling2016

    • Author(s)
      Fujino, T.; Hinoue, T.; Usuki, Y.; Satoh, T.
    • Journal Title

      Org. Lett.

      Volume: 18 Issue: 21 Pages: 5688-5691

    • DOI

      10.1021/acs.orglett.6b02919

    • NAID

      120006493279

    • URL

      https://ocu-omu.repo.nii.ac.jp/records/2020131

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Ruthenium-Catalyzed Cross-Coupling of Maleimides with Alkenes2016

    • Author(s)
      Morita, T.; Akita, M.; Satoh, T.; Kakiuchi, F.; Miura, M.
    • Journal Title

      Org. Lett.

      Volume: 18 Issue: 18 Pages: 4598-4601

    • DOI

      10.1021/acs.orglett.6b02244

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Regioselective Synthesis of Benzophosphole Derivatives via Direct ortho-Alkenylation and Cyclization of Arylthiophosphinamides2016

    • Author(s)
      Unoh, Y.; Yokoyama, Y.; Satoh, T.; Hirano, K.; Miura, M.
    • Journal Title

      Org. Lett.

      Volume: 18 Issue: 20 Pages: 5436-5439

    • DOI

      10.1021/acs.orglett.6b02868

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Synthesis of pai-Conjugated Molecules via Transition-Metal-Catalyzed C-H Functionalization2018

    • Author(s)
      Satoh, T.
    • Organizer
      9th OCARINA International Symposium
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] カルボン酸を始めとする入手容易な分子の触媒的変換反応の開発2017

    • Author(s)
      佐藤哲也
    • Organizer
      新学術領域研究「精密制御反応場」第2回公開シンポジウム
    • Place of Presentation
      名古屋大学(愛知県・名古屋市)
    • Year and Date
      2017-01-25
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] Transition-Metal-Catalyzed Regioselective C-H Functionalization2017

    • Author(s)
      Satoh, T.
    • Organizer
      International Symposium on Pure & Applied Chemistry 2017
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 遷移金属錯体触媒を用いる炭素ー水素結合の直接誘導体化法の開発2017

    • Author(s)
      Satoh, T.
    • Organizer
      先端錯体工学研究会年会
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] 環境に優しい低エミッション型脱水素クロスカップリング反応の開発2017

    • Author(s)
      Satoh, T.
    • Organizer
      JACI/JST交流セミナー
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] クロスカップリング入門2017

    • Author(s)
      Satoh, T.
    • Organizer
      大阪市立大学文化交流センター講座「温故知新」
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] Transition-Metal-Catalyzed Transformation of Benzoic Acids and Related Compounds2016

    • Author(s)
      Satoh, T.
    • Organizer
      International Symposium on C-O Activation
    • Place of Presentation
      姫路商工会議所(兵庫県・姫路市)
    • Year and Date
      2016-10-25
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis of Difluorinated Enyne Derivatives via Sonogashira-type Coupling2016

    • Author(s)
      Fujino, T.; Hinoue, T.; Usuki, Y.; Satoh, T.
    • Organizer
      International Symposium on C-O Activation
    • Place of Presentation
      姫路商工会議所(兵庫県・姫路市)
    • Year and Date
      2016-10-25
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Silver-Mediated Addition of Carboxylic Acids to Alkynes2016

    • Author(s)
      Kikui, N.; Hinoue, T.; Usuki, Y.; Satoh, T.
    • Organizer
      International Symposium on C-O Activation
    • Place of Presentation
      姫路商工会議所(兵庫県・姫路市)
    • Year and Date
      2016-10-25
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Rh(III)-catalyzed C-H Bond Arylation of Arylthiophosphinamides2016

    • Author(s)
      Unoh, Y.; Hirano, K.; Satoh, T.; Miura, M.
    • Organizer
      6th Junior International Conference on Cutting-Edge Organic Chemistry in Asia
    • Place of Presentation
      九州大学(福岡県・春日市)
    • Year and Date
      2016-10-24
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Rhodium(III)-Catalyzed Regioselective C-H Functionalization2016

    • Author(s)
      Satoh, T.
    • Organizer
      3rd International Conference on Organometallics and Catalysis
    • Place of Presentation
      Seoul (South Korea)
    • Year and Date
      2016-08-28
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Straightforward Synthesis of Biarylphosphine Derivatives via Rh(III)-catalyzed C-H Bond Functionalization2016

    • Author(s)
      Unoh, Y.; Satoh, T.; Hirano, K.; Miura, M.
    • Organizer
      27th International Conference on Organometallic Chemistry
    • Place of Presentation
      Melbourne (Australia)
    • Year and Date
      2016-07-17
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ロジウム(III)触媒を用いる脱水素カップリング反応2016

    • Author(s)
      佐藤哲也
    • Organizer
      第49回有機金属若手の会 夏の学校
    • Place of Presentation
      東海大学嬬恋高原研修センター(群馬県・吾妻郡嬬恋村)
    • Year and Date
      2016-07-11
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] Synthesis of Fused Furan Compounds via Palladium(II)-Catalyzed Intramolecular Dehydrocyclization2016

    • Author(s)
      Kaida, H.; Hirano, K.; Satoh, T.; Miura, M.
    • Organizer
      20th International Symposium on Homogeneous Catalysis
    • Place of Presentation
      京都テルサ(京都府・京都市)
    • Year and Date
      2016-07-10
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Direct C-H Alkenylation of Thienothiophene and Related Fused Heteroarenes under Palladium Catalysis2016

    • Author(s)
      Morita, T.; Satoh, T.; Miura, M.
    • Organizer
      20th International Symposium on Homogeneous Catalysis
    • Place of Presentation
      京都テルサ(京都府・京都市)
    • Year and Date
      2016-07-10
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Ruthenium-Catalyzed C1- and C7-Selective Acetoxylation of Carbazole and Indole Derivatives via C-H Bond Cleavage2016

    • Author(s)
      Okada, T.; Satoh, T.; Miura, M.
    • Organizer
      20th International Symposium on Homogeneous Catalysis
    • Place of Presentation
      京都テルサ(京都府・京都市)
    • Year and Date
      2016-07-10
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 含ヘテロ原子配向基を利用したC-H官能基化反応2016

    • Author(s)
      佐藤哲也
    • Organizer
      ヘテロ原子部会平成28年度第1回懇話会
    • Place of Presentation
      大阪府立大学(大阪府・堺市)
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Book] Rhodium Catalysis in Organic Synthesis: Methods and Reactions2018

    • Author(s)
      Satoh, T.; Miura, M.
    • Publisher
      Wiley
    • Related Report
      2017 Annual Research Report
  • [Book] Science of Synthesis (Vol. Catalytic Transformations via C-H Activation 1)2016

    • Author(s)
      Satoh, T.; Miura, M.
    • Total Pages
      32
    • Publisher
      Georg Thieme
    • Related Report
      2016 Annual Research Report
  • [Book] Cleavage of Carbon-Carbon Single Bonds by Transition Metals2016

    • Author(s)
      Satoh, T.; Miura, M.
    • Total Pages
      45
    • Publisher
      Wiley-VCH
    • Related Report
      2016 Annual Research Report

URL: 

Published: 2016-04-26   Modified: 2018-12-17  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi