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Development of New Methods for Catalytic Organic Synthesis via Chain Walking

Research Project

Project/Area Number 25708019
Research Category

Grant-in-Aid for Young Scientists (A)

Allocation TypePartial Multi-year Fund
Research Field Synthetic chemistry
Research InstitutionKeio University

Principal Investigator

Kochi Takuya  慶應義塾大学, 理工学部, 講師 (70396779)

Project Period (FY) 2013-04-01 – 2017-03-31
Project Status Completed (Fiscal Year 2016)
Budget Amount *help
¥26,780,000 (Direct Cost: ¥20,600,000、Indirect Cost: ¥6,180,000)
Fiscal Year 2015: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2014: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2013: ¥18,460,000 (Direct Cost: ¥14,200,000、Indirect Cost: ¥4,260,000)
Keywordsパラジウム触媒 / 環化反応 / チェーンウォーキング / 有機合成 / 五員環形成反応 / 1,n-ジエン / ヒドロシリル化 / アルケン異性化反応 / βアセトキシ脱離 / アリール化 / 選択的異性化反応 / 末端アルケン / シリルエノールエーテル / ヒドロシリル化反応 / シクロペンタン誘導体 / 環化異性化反応
Outline of Final Research Achievements

As a method to introduce a functional group at the reaction initiation site in the palladium-catalyzed chain-walking cycloisomerization of 1,n-dienes, we developed a cyclization/hydrosilylation of 1,n-dienes via chain-walking. In the presence of palladium catalysts, the reaction of various 1,n-dienes with hydrosilanes proceeded to give products formed by five-membered ring formation after the introduction of a silyl group, followed by chain walking. We also investigated on how to control the position of the alkene formed after the chain-walking process and found that the use of siloxy groups to form silyl enol ethers was effective for settling the position of the alkene after chain walking.

Report

(5 results)
  • 2016 Annual Research Report   Final Research Report ( PDF )
  • 2015 Annual Research Report
  • 2014 Annual Research Report
  • 2013 Annual Research Report
  • Research Products

    (21 results)

All 2017 2016 2015 2014

All Journal Article (2 results) (of which Peer Reviewed: 2 results,  Acknowledgement Compliant: 2 results) Presentation (19 results) (of which Int'l Joint Research: 7 results,  Invited: 2 results)

  • [Journal Article] Chain-walking Cycloisomerization of 1,n-Dienes Catalyzed by Pyridine-Oxazoline Palladium Catalysts and Its Application to Asymmetric Synthesis2016

    • Author(s)
      Taro Hamasaki, Fumitoshi Kakiuchi, Takuya Kochi
    • Journal Title

      Chemistry Letters

      Volume: 45 Issue: 3 Pages: 297-299

    • DOI

      10.1246/cl.151138

    • NAID

      130005132156

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Chain Walking as a Strategy for Carbon-Carbon Bond Formation at Unreactive Sites in Organic Synthesis: Catalytic Cycloisomerization of Various 1,n-Dienes2015

    • Author(s)
      Taro Hamasaki, Yuka Aoyama, Junichi Kawasaki, Fumitoshi Kakiuchi, Takuya Kochi
    • Journal Title

      Journal of the American Chemical Society

      Volume: 137 Issue: 51 Pages: 16163-16171

    • DOI

      10.1021/jacs.5b10804

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] パラジウム触媒による離れた位置にアセトキシ基を有するアルケン類のチェーンウォーキングを経るアリール化反応2017

    • Author(s)
      熊谷貴明、垣内史敏、河内卓彌
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾大学(神奈川県・横浜市)
    • Year and Date
      2017-03-17
    • Related Report
      2016 Annual Research Report
  • [Presentation] 革新的な物質活性化法を駆使した新しい触媒的分子変換法の開発2016

    • Author(s)
      河内卓彌
    • Organizer
      第33回有機合成化学セミナー
    • Place of Presentation
      ヒルトンニセコビレッジ(北海道・ニセコ町)
    • Year and Date
      2016-09-07
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] アセトキシ基をもつアルケン類のパラジウム触媒によるチェーンウォーキングを経るアリール化反応2016

    • Author(s)
      熊谷貴明、垣内史敏、河内卓彌
    • Organizer
      第33回有機合成化学セミナー
    • Place of Presentation
      ヒルトンニセコビレッジ(北海道・ニセコ町)
    • Year and Date
      2016-09-07
    • Related Report
      2016 Annual Research Report
  • [Presentation] ピリジン-オキサゾリンパラジウム触媒を用いたチェーンウォーキングを経る1,n-ジエンの環化異性化反応2016

    • Author(s)
      浜崎太郎・垣内史敏・河内卓彌
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      同志社大学京田辺キャンパス(京都府・京田辺市)
    • Year and Date
      2016-03-26
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Chain Walking as a Strategy for Catalytic Organic Synthesis2015

    • Author(s)
      Takuya Kochi
    • Organizer
      The 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem 2015)
    • Place of Presentation
      Hilton Hawaiian Village(アメリカ合衆国)
    • Year and Date
      2015-12-16
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Five-Membered Ring Construction via Chain-Walking Cycloisomerization of Various 1,n-Dienes Catalyzed by Palladium Complexes2015

    • Author(s)
      Taro Hamasaki, Fumitoshi Kakiuchi, and Takuya Kochi
    • Organizer
      The 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem 2015)
    • Place of Presentation
      Hawaii Convention Center(アメリカ合衆国)
    • Year and Date
      2015-12-16
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Palladium-Catalyzed Selective Olefin Isomerization via Chain Walking2015

    • Author(s)
      Yuya Yamasaki, Fumitoshi Kakiuchi, and Takuya Kochi
    • Organizer
      The 2015 International Chemical Congress of Pacific Basin Societies (Pacifichem 2015)
    • Place of Presentation
      Hawaii Convention Center(アメリカ合衆国)
    • Year and Date
      2015-12-16
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Palladium-Catalyzed Cycloisomerization and Hydrosilylation/Cyclization of 1,n-Dienes via Chain Walking2015

    • Author(s)
      Takuya Kochi, Taro Hamasaki, Kazuya Ichinose, and Fumitoshi Kakiuchi
    • Organizer
      the 13th International Kyoto Conference on New Aspects of Organic Chemistry (IKCOC-13)
    • Place of Presentation
      リーガロイヤルホテル京都(京都府・京都市)
    • Year and Date
      2015-11-12
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] パラジウム触媒によるチェーンウォーキングを利用したアルケンの選択的異性化反応2015

    • Author(s)
      山﨑裕也・垣内史敏・河内卓彌
    • Organizer
      第62回有機金属化学討論会
    • Place of Presentation
      関西大学千里山キャンパス(大阪府・吹田市)
    • Year and Date
      2015-09-08
    • Related Report
      2015 Annual Research Report
  • [Presentation] Palladium-Catalyzed Olefin Isomerization via Chain Walking2015

    • Author(s)
      Yuya Yamasaki, Fumitoshi Kakiuchi, and Takuya Kochi
    • Organizer
      the 7th International Conference on Green and Sustainable Chemistry (GSC-7) and 4th JACI/GSC Symposium
    • Place of Presentation
      一橋大学一橋講堂(東京都・千代田区)
    • Year and Date
      2015-07-08
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Catalytic Cycloisomerization of Various 1,n-Dienes via Chain Walking by Using Palladium Complexes2015

    • Author(s)
      Taro Hamasaki, Fumitoshi Kakiuchi, and Takuya Kochi
    • Organizer
      the 7th International Conference on Green and Sustainable Chemistry (GSC-7) and 4th JACI/GSC Symposium
    • Place of Presentation
      一橋大学一橋講堂(東京都・千代田区)
    • Year and Date
      2015-07-08
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] フェナントロリンパラジウム触媒を用いたチェーンウォーキングを経るアルケンの異性化反応2015

    • Author(s)
      山﨑裕也、垣内史敏、河内卓彌
    • Organizer
      日本化学会第95春季年会
    • Place of Presentation
      日本大学理工学部船橋キャンパス/薬学部(千葉県・船橋市)
    • Year and Date
      2015-03-28
    • Related Report
      2014 Annual Research Report
  • [Presentation] パラジウム触媒を用いたチェーンウォーキングを経るタンデム型環化・ヒドロシリル化反応による五員環構築法の開発2014

    • Author(s)
      市瀬和也、濵﨑太郎、垣内史敏、河内卓彌
    • Organizer
      第68回有機合成化学協会関東支部シンポシウム
    • Place of Presentation
      新潟大学五十嵐キャンパス(新潟県・新潟市)
    • Year and Date
      2014-11-30
    • Related Report
      2014 Annual Research Report
  • [Presentation] チェーンウォーキングを経る1,n-ジエンの触媒的タンデム型環化/ヒドロシリル化による五員環構築2014

    • Author(s)
      河内卓彌・市瀬和也・濵﨑太郎・垣内史敏
    • Organizer
      第61回有機金属化学討論会
    • Place of Presentation
      九州大学病院キャンパス(福岡県・福岡市)
    • Year and Date
      2014-09-23
    • Related Report
      2014 Annual Research Report
  • [Presentation] Chain-Walking as a Strategy for Organic Synthesis: Catalytic Five-Membered Ring Formation from Various 1,n-Dienes2014

    • Author(s)
      Takuya Kochi, Taro Hamasaki, Kazuya Ichinose, Fumitoshi Kakiuchi
    • Organizer
      the 19th International Symposium on Homogeneous Catalysis (ISHC-XIX)
    • Place of Presentation
      Ottawa Convention Centre(カナダ)
    • Year and Date
      2014-07-10
    • Related Report
      2014 Annual Research Report
  • [Presentation] パラジウム触媒を用いたチェーンウォーキングを経る1,n-ジエンのタンデム型環化異性化/ヒドロシリル化反応2014

    • Author(s)
      市瀬和也、浜崎太郎、垣内史敏、河内卓彌
    • Organizer
      新学術領域研究分子活性化-有機分子触媒合同シンポシウム
    • Place of Presentation
      北海道大学学術交流会館(北海道・札幌市)
    • Year and Date
      2014-06-20
    • Related Report
      2014 Annual Research Report
  • [Presentation] パラジウム触媒を用いたチェーンウォーキングを経る1,n-ジエンの環化異性化・ヒドロシリル化反応2014

    • Author(s)
      市瀬和也、浜崎太郎、垣内史敏、河内卓彌
    • Organizer
      第3回JACI/GSCシンポジウム
    • Place of Presentation
      東京国際フォーラム(東京都・千代田区)
    • Year and Date
      2014-05-23
    • Related Report
      2014 Annual Research Report
  • [Presentation] パラジウム触媒によるチェーンウォーキングを経る末端オレフィンの選択的異性化反応2014

    • Author(s)
      山﨑裕也、濵﨑太郎、垣内史敏、河内卓彌
    • Organizer
      第67 回有機合成化学協会関東支部シンポシウム
    • Place of Presentation
      慶應義塾大学矢上キャンパス(神奈川県・横浜市)
    • Year and Date
      2014-05-17
    • Related Report
      2014 Annual Research Report
  • [Presentation] チェーンウォーキングを経る1,n-ジエンのタンデム型環化異性化/ヒドロシリル化反応2014

    • Author(s)
      市瀬和也・浜崎太郎・垣内史敏・河内卓彌
    • Organizer
      日本化学会第94春季年会
    • Place of Presentation
      名古屋大学東山キャンパス
    • Related Report
      2013 Annual Research Report

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Published: 2013-05-21   Modified: 2019-07-29  

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