Development of Innovative Cycloisomerization of Dienes via Chain Walking

• Project/Area Number: 24655088
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Synthetic chemistry
• Research Institution: Keio University
• Principal Investigator: TAKUYA Kochi 慶應義塾大学, 理工学部, 講師 (70396779)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2014: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2013: ¥1,300,000 (Direct Cost: ¥1,000,000、Indirect Cost: ¥300,000); Fiscal Year 2012: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
• Keywords: チェーンウォーキング / 環化異性化 / パラジウム触媒 / 五員環化合物 / ジエン / 1,10-フェナントロリン配位子 / 炭素－炭素結合生成 / 環化異性化反応 / シクロペンタン誘導体 / 合成化学 / 触媒・化学プロセス / 有機化学

Outline of Final Research Achievements

Chain walking is a mechanism where a metal species looks like moving around on a carbon chain and has been utilized in syntheses of polyolefins having novel structures. However, syntheses of relatively small organic molecules using this mechanism have rarely been investigated. In this research, synthesis of small organic molecules using carbon-carbon bond formation via chain walking was achieved for cycloisomerization of dienes. This reaction is applicable to various 1,n-dienes and mechanistic investigations indicated that the reaction proceeds via a chain-walking mechanism.

Research Products

• [Journal Article] Chain-Walking Strategy for Organic Synthesis: Catalytic Cycloisomerization of 1,n-Dienes (2012)
  • Author(s): Takuya Kochi, Taro Hamasaki, Yuka Aoyama, Junichi Kawasaki, and Fumitoshi Kakiuchi
  • Journal Title: Journal of the American Chemical Society Volume: 134 Issue: 40 Pages: 16544-16547
  • DOI: 10.1021/ja308377u
  • Peer Reviewed
• [Presentation] Five-Membered Ring Formation by Chain-Walking Cycloisomerization of Various 1,n-Dienes (2014)
  • Author(s): Taro Hamasaki, Fumitoshi Kakiuchi, Takuya Kochi
  • Organizer: the 2nd International Conference on Organometallics and Catalysis (OM&cat-2014)
  • Place of Presentation: Todaiji Temple Cultural Center（奈良県・奈良市）
  • Year and Date: 2014-10-28
• [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様々な1,n-ジエン類の環化異性化反応 (2014)
  • Author(s): 濵﨑太郎、垣内史敏、河内卓彌
  • Organizer: 第31回有機合成化学セミナー
  • Place of Presentation: 休暇村志賀島（福岡県・福岡市）
  • Year and Date: 2014-09-17
• [Presentation] Chain-Walking Cycloisomerization of Various 1,n-Dienes Catalyzed by Palladium Complexes (2014)
  • Author(s): Taro Hamasaki, Fumitoshi Kakiuchi, Takuya Kochi
  • Organizer: the XXVI International Conference on Organometallic Chemistry (ICOMC 2014)
  • Place of Presentation: Royton Sapporo（北海道・札幌市）
  • Year and Date: 2014-07-17
• [Presentation] Synthesis of Cyclic Compounds by Cycloisomerization of Various 1,n-Dienes via Chain Walking (2014)
  • Author(s): Taro Hamasaki, Fumitoshi Kakiuchi, and Takuya Kochi
  • 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
• [Presentation] Palladium-Catalyzed Cycloisomerization of Various Dienes via Chain-Walking (2013)
  • Author(s): Taro Hamasaki, Yuka Aoyama, Junichi Kawasaki, Fumitoshi Kakiuchi, and Takuya Kochi
  • Organizer: the 20th EuCheMS Conference on Organometallic Chemistry (EUCOMC XX)
  • Place of Presentation: University of St. Andrews
• [Presentation] Cycloisomerization of 1,n-dienes via chain walking catalyzed by palladium complexes (2013)
  • Author(s): Taro Hamasaki, Yuka Aoyama, Junichi Kawasaki, Fumitoshi Kakiuchi, and Takuya Kochi
  • Organizer: The Sixteenth International Symposium on Relations between Homogeneous and Heterogeneous Catalysis (ISHHC-16)
  • Place of Presentation: Conference Hall, Hokkaido University
• [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様々な1,n-ジエン類の環化異性化反応
  • Author(s): 濵﨑太郎、垣内史敏、河内卓彌
  • Organizer: 第66回有機合成化学協会関東支部シンポシウム
  • Place of Presentation: 東京工業大学大岡山キャンパス
• [Presentation] チェーンウォーキングを利用したsp3炭素上での炭素－炭素結合生成を経る1,n-ジエン類の触媒的環化異性化反応
  • Author(s): ○浜崎太郎・河内卓彌・青山由果・河崎純一・垣内史敏
  • Organizer: 第1回JACI/GSCシンポジウム
  • Place of Presentation: 東京
• [Presentation] Chain-Walking Strategy for Catalytic Cycloisomerization of 1,n-Dienes
  • Author(s): ○Takuya Kochi, Taro Hamasaki, Yuka Aoyama, Junichi Kawasaki, Fumitoshi Kakiuchi
  • Organizer: XXV International Conference on Organometallic Chemistry
  • Place of Presentation: Lisbon, Portugal
• [Presentation] Pd-Catalyzed Chain-Walking Cycloisomerization of 1,n-Dienes
  • Author(s): ○Taro Hamasaki, Yuka Aoyama, Junichi Kawasaki, Fumitoshi Kakiuchi, Takuya Kochi
  • Organizer: the Twelfth International Kyoto Conference on New Aspects of Organic Chemistry
  • Place of Presentation: 京都
• [Presentation] チェーンウォーキングを経る非環状1,n-ジエンの環化異性化反応
  • Author(s): ○濵﨑太郎・垣内史敏・河内卓彌
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 草津