Development of Iron-Catalyzed Addition of Organometallic Compoundsto Alkynes

• Project/Area Number: 22605005
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: 元素戦略
• Research Institution: Kyoto University
• Principal Investigator: SHIRAKAWA Eiji 京都大学, 大学院・理学研究科, 准教授 (70273472)
• Project Period (FY): 2010 – 2012
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥4,550,000 (Direct Cost: ¥3,500,000、Indirect Cost: ¥1,050,000); Fiscal Year 2012: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2011: ¥780,000 (Direct Cost: ¥600,000、Indirect Cost: ¥180,000); Fiscal Year 2010: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
• Keywords: 付加反応 / 有機リチウム / Grignard 反応剤 / チタン触媒 / 亜鉛触媒 / 協同触媒系 / アルキルメタル / 異性化反応 / 鉄触媒 / カルボメタル化 / アルキン / 有機金属化合物 / 不飽和炭化水素

Research Abstract

Iron catalysts were found to be effective for otherwise unattainable aryl- and alkenylmetalation of alkynes with organolithium compounds. o-(Trimethylsilyl)phenyllithium was converted to benzosilole derivatives, which are known to have a wide application in optoelectronic area. In addition, the reaction of terminal alkenes with cyclopentylmagnesium bromide under iron-copper cooperative catalysis was found to give primary Grignard reagents.

Research Products

• [Journal Article] Iron-Copper Cooperative Catalysis in the Reactions of Alkyl Grignard Reagents: Exchange Reaction with Alkenes and Carbometalation of Alkynes (2012)
  • Author(s): Eiji Shirakawa, Daiji Ikeda, Seiji Masui, Masatoshi Yoshida, Tamio Hayashi
  • Journal Title: J. Am. Chem. Soc Volume: Vol. 134, No. 1 Issue: 1 Pages: 272-279
  • DOI: 10.1021/ja206745w
  • Peer Reviewed
• [Journal Article] Iron-Catalyzed Aryl- and Alkenyllithiation of Alkynes and Its Application to Benzosilole Synthesis (2011)
  • Author(s): Eiji Shirakawa, Seiji Masui, Rintaro Narui, Ryo Watabe, Daiji Ikeda, Tamio Hayashi
  • Journal Title: Chem. Commun Volume: Vol. 47, No. 34 Issue: 34 Pages: 9714-9716
  • DOI: 10.1039/c1cc11989c
  • Peer Reviewed
• [Presentation] チタン-亜鉛協同触媒系を用いるアルキルGrignard 反応剤の異性化 (2012)
  • Author(s): 白川英二,増井誠二,林 民生
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 横浜
  • Year and Date: 2012-03-28
• [Presentation] Reactions of Grignard Reagents Catalyzed Cooperatively by Iron and Copper Complexes (2011)
  • Author(s): Eiji Shirakawa, Tamio Hayashi
  • Organizer: The 14th Asian Chemical Congress
  • Place of Presentation: Bangkok, Thailand
  • Year and Date: 2011-09-08
• [Presentation] Reactions of Grignard Reagents Catalyzed Cooperatively by Iron and Copper Complexes (2011)
  • Author(s): Eiji Shirakawa, Tamio Hayashi
  • Organizer: 14th Asian Chemical Congress
  • Place of Presentation: Bangkok, Thailand.
  • Year and Date: 2011-09-04
• [Presentation] 鉄触媒によるアルキンのアリールリチウム化を用いたベンゾシロールの合成 (2011)
  • Author(s): 白川英二,増井誠二,渡部 遼,成井倫太郎,池田大次,林 民生
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 横浜
  • Year and Date: 2011-03-29
• [Presentation] 鉄触媒によるアルキンのアリールリチウム化を用いたベンゾシロールの合成 (2011)
  • Author(s): 白川英二
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 日本化学会第91春期年会(2011)講演予稿集
  • Year and Date: 2011-03-11
• [Presentation] Reactions of Grignard Reagents Catalyzed Cooperatively by Iron and Copper Complexes (2010)
  • Author(s): Eiji Shirakawa, Tamio Hayashi
  • Organizer: Pacifichem 2010
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2010-12-17
• [Presentation] Reactions of Grignard Reagents Catalyzed Cooperatively by Iron and Copper Complexes (2010)
  • Author(s): 白川英二
  • Organizer: Pacifichem2010, Symposium on Cooperative Catalysis
  • Place of Presentation: The Hilton Hawaiian Village (Honolulu, USA)(招待講演)
  • Year and Date: 2010-12-17