Development of universal cross-coupling reactions under cobalt catalysis

• Project/Area Number: 18205012
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Kyoto University
• Principal Investigator: OSHIMA Koichiro (KOICHIRO Oshima) Kyoto University, 大学院・工学研究科, 教授 (00111922)
• Co-Investigator(Kenkyū-buntansha): YORIMITSU Hideki 京都大学, 大学院・理学研究科, 准教授 (00372566)
• Project Period (FY): 2006 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥50,700,000 (Direct Cost: ¥39,000,000、Indirect Cost: ¥11,700,000); Fiscal Year 2009: ¥9,880,000 (Direct Cost: ¥7,600,000、Indirect Cost: ¥2,280,000); Fiscal Year 2008: ¥9,880,000 (Direct Cost: ¥7,600,000、Indirect Cost: ¥2,280,000); Fiscal Year 2007: ¥9,880,000 (Direct Cost: ¥7,600,000、Indirect Cost: ¥2,280,000); Fiscal Year 2006: ¥21,060,000 (Direct Cost: ¥16,200,000、Indirect Cost: ¥4,860,000)
• Keywords: 選択的合成 / 反応 / コバルト / 交差カップリング反応 / カルボメタル化 / 有機亜鉛反応剤 / 付加反応 / ラジカル / ハロゲン化アルキル / 脱離反応 / 交差カップリング / ハロアセタール

Research Abstract

New cobalt-catalyzed cross-coupling reactions of alkyl halides with organometallic reagents have been developed. The reactions contribute to the establishment of universal cross-coupling reaction to connect arbitrary carbon-carbon bonds. Novel dehydrohalogenation is also developed, realizing selective synthesis of alkenes. The concept of cobalt catalysis can be extended to other transition metals group 8 to 11.

Research Products

• [Journal Article] Silver-Catalyzed Diallylation and Dibenzylation of gem-Dibromoalkanes with Grignard Reagents (2010)
  • Author(s): Yukihiro Mitamura, Hidenori Someya, Hideki Yorimitsu, Koichiro Oshima
  • Journal Title: Synlett Pages: 309-312
  • Peer Reviewed
• [Journal Article] Metal-Mediated Retro-Allylation of Homoallyl Alcohols for Highly Selective Organic Synthesis. (2009)
  • Author(s): Hideki Yorimitsu, Koichiro Oshima
  • Journal Title: Bull. Chem. Soc. Jpn. 82 Pages: 778-792
  • NAID: 10025125733
  • Peer Reviewed
• [Journal Article] Copper-Catalyzed Allylation of Alkyl Halides with Allylic Grignard Reagents (2009)
  • Author(s): Masahiro Sai, Hideki Yormitsu, Koichiro Osdhima
  • Journal Title: Bull.Chem.Soc.Jpn. 82 Pages: 1194-1196
  • Peer Reviewed
• [Journal Article] Cobalt-Catalyzed Regioselective Dehydrohal-ogenation of Alkyl Halides with Dimethylphenylsilylmethylmagnesium Chloride. (2008)
  • Author(s): Tsuneyuki Kobayashi, Hirohisa Ohmiya, Hideki Yorimitsu, Koichiro Oshima
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 11276-11277
  • Peer Reviewed
• [Journal Article] Silver-Catalyzed Benzylation and Allylation Reactions of Tertiary and Secondary Alkyl Halides with Grignard Reagents. (2008)
  • Author(s): Hidenori Someya, Hirohisa Ohmiya, Hideki Yorimitsu, Koichiro Oshima
  • Journal Title: Org. Lett. 10 Pages: 969-971
  • Peer Reviewed
• [Journal Article] Highly Selective Synthetic Reactions by the Combined Use of Organometallic Reagents and Radical Species. (2008)
  • Author(s): Koichiro Oshima
  • Journal Title: Bull. Chem. Soc. Jpn. 81 Pages: 1-24
  • Peer Reviewed
• [Journal Article] Cobalt-Catalyzed Regioselective Dehydrohalogenation of Alkyl Halides with Dimethylphenylsilylmethylmagnesium Chloride (2008)
  • Author(s): Tsuneyuki Kobayashi, Hirohisa Ohmiya, Hideki Yorimitsu and Koichiro Oshima
  • Journal Title: J. Am. Chem. Soc 130 Pages: 11276-11277
• [Journal Article] Silver-Catalyzed Transmetalation between Chlorosilanes and Aryl and Alkenyl Grignard Reagents for Synthesis of Tetraorganosilanes (2008)
  • Author(s): Kei Murakami, Koji Hirano, Hideki Yorimitsu and Koichiro Oshima
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 5833-5835
• [Journal Article] Cobalt-Catalyzed Regioselective Dehydrohalogenation of Alkyl Halides with Dimethylphenylsilylmethylmagnesium Chloride (2008)
  • Author(s): Kobayashi, T., Ohmiya, H., Yorimitsu, H, Oshima, K.
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 11276-11277
  • Peer Reviewed
• [Journal Article] Cobalt-Catalyzed Cross-Coupling Reactions of Aryl Bromides with Alkyl Grignard Reagents (2008)
  • Author(s): Hamaguchi, H., Uemura, M., Yasui, H., Yorimitsu, H., Oshima, K.
  • Journal Title: Chem. Lett. 37 Pages: 1178-1179
  • NAID: 10024397323
  • Peer Reviewed
• [Journal Article] Vanadium-Catalyzed Cross-Coupling Reactions of Alkyl Halides with Aryl Grignard Reagents (2008)
  • Author(s): Shigeo Yasuda, Hideki Yorimitsu, and Koichiro Oshima
  • Journal Title: Bulletin of the Chemical Society of Japan 81 Pages: 287-290
  • NAID: 10021073738
• [Journal Article] Cobalt-Catalyzed Sequential Cyclization/Cross-Coupling Reactions of 6-Halo-1-hexene Derivatives with Grignard Reagents and Their Application to the Synthesis of 1,3-Diols (2007)
  • Author(s): Hidenori Someya, Hirohisa Ohmiya, Hideki Yorimitsu, and Koichiro Oshima
  • Journal Title: Tetrahedron 63 Pages: 8609-8618
  • NAID: 120001749567
• [Journal Article] Chromium-Catalyzed Arylmagnesiation of Alkynes (2007)
  • Author(s): Kei Murakami, Hirohisa Ohmiya, Hideki Yorimitsu and Koichiro Oshima
  • Journal Title: Org. Lett. 9 Pages: 1569-1571
• [Journal Article] N-Heterocyclic Carbene Ligands in Cobalt-Catalyzed Sequential Cyclization/Cross-Coupling Reactions of 6-Halo-1-hexene Derivatives with Grignard Reagents (2007)
  • Author(s): Hidenori Someya, Hirohisa Ohmiya, Hideki Yorimitsu and Koichiro Oshima
  • Journal Title: Org. Lett. 9 Pages: 1565-1567
• [Journal Article] N-Heterocyclic Carbene Ligands in Cobalt-Catalyzed Sequential Cyclization/Cross-Coupling Reactions of 6-Halo-1-hexene Derivatives with Grignard Reagents (2007)
  • Author(s): Hidenori Someya, Hirohisa Ohmiya, Hideki Yorimitsu, and Koichiro Oshima
  • Journal Title: Organic Letters 9 Pages: 1565-1567
• [Journal Article] Chromium-Catalyzed Arylmagnesiation of Alkynes (2007)
  • Author(s): Kei Murakami, Hirohisa Ohmiya, Hideki Yorimitsu, and Koichiro Oshima
  • Journal Title: Organic Letters 9 Pages: 1565-1567
• [Journal Article] Cobalt-Catalyzed Sequentia1 Cyclization/Cross-Coupling Reactions of 6-Halo-1-hexene Derivatives with Grignard Reagents and Their Application to the Synthesis of 1,3-Diols (2007)
  • Author(s): Hidenori Someya, Hirohisa Ohmiya, Hideki Yorimitsu, and Koichiro Oshima
  • Journal Title: Tetrahedron 63 Pages: 8609-8618
• [Journal Article] New Synthetic Reactions Catalyzed by Cobalt Complexes. (2006)
  • Author(s): Hideki Yorimitsu, Koichiro Oshima
  • Journal Title: Pure Appl. Chem. 78 Pages: 441-449
  • Peer Reviewed
• [Journal Article] Cobalt(diamine)-catalyzed Cross-coupling Reaction of Alkyl Halides with Arylmagnesium Reagents : Stereoselective Constructions of Arylated Asymmetric Carbons and Application to Total Synthesis of AH13205 (2006)
  • Author(s): Hirohisa Ohmiya, Hideki Yorimitsu, Koichiro Oshima
  • Journal Title: Journal of the American Chemical Society 128 Pages: 1886-1889
• [Journal Article] Cobalt-Catalyzed Trimethylsilylmethylmagnesium-Promoted Radical Alkenylation of Alkyl Halides : A Complement to the Heck Reaction (2006)
  • Author(s): Walter Affo, Hirohisa Ohmiya, et al.
  • Journal Title: Journal of the American Chemical Society 128 Pages: 8068-8077
• [Journal Article] Cobalt-mediated Cross-coupling Reactions of Primary and Secondary Alkyl Halides with l-Trimethylsilylethen 1- and 2-Trimethylsilylethynylmagnesium Reagents (2006)
  • Author(s): Hirohisa Ohmiya, Hideki Yorimitsu, Koichiro Oshima
  • Journal Title: Organic Letters 8 Pages: 3093-3096
• [Journal Article] A New Approach to 4-Aryl-1, 3-butanediols by Cobalt-Catalyzed Sequential Radical Cyclization/Arylation Reaction of Silicon-Tethered 6-Iodo-1-hexene Derivatives (2006)
  • Author(s): Hidenori Someya, Azusa Kondoh, Akinori Sato, Hirohisa Ohmiya, Hideki Yorimitsu, Koichiro Oshima
  • Journal Title: Synlett Pages: 3061-3064
• [Presentation] コバルト触媒を用いる有機合成反応 (2010)
  • Author(s): 大嶌幸一郎
  • Organizer: 有機合成新春講演会
  • Place of Presentation: 大阪
  • Year and Date: 2010-01-15
• [Presentation] Selective Reactions Based on Retro-allylation of Homoallyl Alcohols, Asian International Symposium (2009)
  • Author(s): Hideki Yorimitsu
  • Organizer: The 89th Annual Meeting of the Chemical Society of Japan
  • Place of Presentation: Funabashi
  • Year and Date: 2009-03-29
• [Presentation] 有機金属反応剤とラジカル種を複合利用した高選択的有機合成反応の開発 (2008)
  • Author(s): 大鴬幸一郎
  • Organizer: 第25回有機合成化学セミナー
  • Place of Presentation: 熊本
  • Year and Date: 2008-09-08
• [Presentation] Selective Reactions Based on Retro-allylation of Homoallyl Alcohols (2008)
  • Author(s): Hideki Yorimitsu, Koichiro Oshima
  • Organizer: 5th Asian-European Symposium on Metal-Mediated Efficient Organic Synthesis
  • Place of Presentation: Obernai, France
• [Remarks]
  • URL: http://www.mc.kyoto-u.ac.jp/mc2/summary-j.html
• [Remarks]
  • URL: http://www.mc.kyoto-u.ac.jp/mc2/summary-j.html