Research on Catalyst Design by Transition State Control for Efficient Chain Walking

• Project/Area Number: 15KT0069
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Multi-year Fund
• Section: 特設分野
• Research Field: Transition State Control
• Research Institution: Keio University
• Principal Investigator: Kochi Takuya 慶應義塾大学, 理工学部(矢上), 准教授 (70396779)
• Project Period (FY): 2015-07-10 – 2022-03-31
• Project Status: Completed (Fiscal Year 2021)
• Budget Amount: ¥17,810,000 (Direct Cost: ¥13,700,000、Indirect Cost: ¥4,110,000); Fiscal Year 2019: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000); Fiscal Year 2018: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000); Fiscal Year 2017: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000); Fiscal Year 2016: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000); Fiscal Year 2015: ¥8,970,000 (Direct Cost: ¥6,900,000、Indirect Cost: ¥2,070,000)
• Keywords: チェーンウォーキング / パラジウム触媒 / 遷移状態制御 / 理論化学計算 / 実験化学 / アルケン交換 / βヒドリド脱離 / 反応機構 / 重水素 / 移動挿入 / 位置選択性 / 触媒・化学プロセス / 有機金属化学 / 反応機構解析

Outline of Final Research Achievements

Theoretical and experimental investigation on a 1,10-phenanthroline palladium catalyst suggested that chain walking on alkyl chains proceeds more easily than alkene exchange processes. Theoretical examination also indicated that chain walking processes occur with unconventional selectivity, which is supported by experimental investigation using a deuterium-labeled substrate.

Academic Significance and Societal Importance of the Research Achievements

本研究結果により、有機合成化学に変革をもたらす遠隔官能基化技術の一つであるチェーンウォーキングの詳細な理解が深まった。これにより、本手法を利用した有機分子の革新的かつ多様な誘導体合成法やそれに向けた高効率的な触媒の開発が大幅に進むと考えられるため、今後の機能性有機分子およびその開発のための化合物ライブラリーの迅速な創成に役立つと期待できる。

Research Products

• [Journal Article] Remote Arylative Substitution of Alkenes Possessing an Acetoxy Group via β‐Acetoxy Elimination (2021)
  • Author(s): Muto Kazuma、Kumagai Takaaki、Kakiuchi Fumitoshi、Kochi Takuya
  • Journal Title: Angewandte Chemie International Edition Volume: 60 Issue: 46 Pages: 24500-24504
  • DOI: 10.1002/anie.202111396
  • Peer Reviewed
• [Journal Article] Palladium-Catalyzed Remote Diborylative Cyclization of Dienes with Diborons via Chain Walking (2021)
  • Author(s): Kanno Shota、Kakiuchi Fumitoshi、Kochi Takuya
  • Journal Title: Journal of the American Chemical Society Volume: 143 Issue: 46 Pages: 19275-19281
  • DOI: 10.1021/jacs.1c09705
  • Peer Reviewed
• [Journal Article] Nondissociative chain walking as a strategy in catalytic organic synthesis (2019)
  • Author(s): Kochi Takuya、Kanno Shota、Kakiuchi Fumitoshi
  • Journal Title: Tetrahedron Letters Volume: 60 Issue: 37 Pages: 150938-150938
  • DOI: 10.1016/j.tetlet.2019.07.029
  • Peer Reviewed
• [Journal Article] Metal-Catalyzed Sequential Formation of Distant Bonds in Organic Molecules: Palladium-Catalyzed Hydrosilylation/Cyclization of 1,n-Dienes by Chain Walking (2019)
  • Author(s): Kochi Takuya、Ichinose Kazuya、Shigekane Masayuki、Hamasaki Taro、Kakiuchi Fumitoshi
  • Journal Title: Angewandte Chemie International Edition Volume: 58 Issue: 16 Pages: 5261-5265
  • DOI: 10.1002/anie.201814558
  • Peer Reviewed
• [Journal Article] Selective Long-Distance Isomerization of Terminal Alkenes via Nondissociative Chain Walking (2018)
  • Author(s): Yamasaki Yuya、Kumagai Takaaki、Kanno Shota、Kakiuchi Fumitoshi、Kochi Takuya
  • Journal Title: The Journal of Organic Chemistry Volume: 83 Issue: 16 Pages: 9322-9333
  • DOI: 10.1021/acs.joc.8b01288
  • Peer Reviewed
• [Presentation] 1,10-フェナントロリンパラジウム触媒のチェーンウォーキング過程の機構に関する理論化学的解析 (2021)
  • Author(s): 武藤 一馬、畑中 美穂、垣内 史敏、河内 卓彌
  • Organizer: 日本化学会第101春季年会
• [Presentation] チェーンウォーキングを経る末端アルケン選択的な長距離異性化反応 (2019)
  • Author(s): 菅野翔太、山﨑裕也、熊谷貴明、垣内史敏、河内卓彌
  • Organizer: 第115回有機合成シンポジウム
• [Presentation] チェーンウォーキングを経るアルケンの選択的長距離異性化によるシリルエノールエーテルの合成 (2019)
  • Author(s): 菅野翔太、山﨑裕也、熊谷貴明、垣内史敏、河内卓彌
  • Organizer: 第8回JACI/GSCシンポジウム
• [Presentation] Chain Walking as a Strategy for Catalytic Organic Synthesis (2017)
  • Author(s): Kochi, T.
  • Organizer: The 2nd International Symposium on Precisely Designed Catalysts with Customized Scaffolding
  • Int'l Joint Research / Invited
• [Presentation] Chain Walking as a Novel Strategy for Syntheses of Cyclic Organic Molecules from Various 1,n-Dienes (2017)
  • Author(s): Kochi, T.; Hamasaki, T.; Ichinose, K.; Kakiuchi, F.
  • Organizer: The 19th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 19)
  • Int'l Joint Research
• [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
  • Invited