Development of New Acylation Reactions via Aromatic Carbon-Hydrogen Bond Cleavaege by Transition Metal Catalysts

• Project/Area Number: 22750096
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Keio University
• Principal Investigator: KOCHI Takuya 慶應義塾大学, 理工学部, 講師 (70396779)
• Project Period (FY): 2010 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000); Fiscal Year 2011: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000); Fiscal Year 2010: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
• Keywords: ルテニウム触媒 / 炭素-水素結合切断 / 炭素-炭素結合形成 / アシル化 / ピリジン誘導体 / キレート形成 / 酸塩化物 / カルボニル化合物 / 炭素-水素結合官能基化 / エノン / ジアリールケトン

Research Abstract

Catalytic functionalization via cleavage of unreactive carbon-hydrogen bonds by transition metal complexes has been widely studied in recent years. As a new method in this class of reactions, we developed a reaction for catalytic introduction of acyl groups using acyl chlorides. When arylpyridines are reacted with acyl chlorides such as benzoyl chlorides and alkenoyl chlorides, ortho-selective acylation proceeded to give benzophenone and enone derivatives.

Research Products

• [Journal Article] Ruthenium-catalyzed acylation of arylpyridines with acyl chlorides via ortho-selective C. H bond cleavage (2011)
  • Author(s): Takuya Kochi, Aoi Tazawa, Kazuki Honda, and Fumitoshi Kakiuchi
  • Journal Title: Chemistry Letters Volume: 40巻 Pages: 1018-1020
  • NAID: 10029522752
  • Peer Reviewed
• [Journal Article] Ruthenium-catalyzed conversion of sp3 C. O bonds in ethers to C. C bonds using triarylboroxins (2011)
  • Author(s): Yohei Ogiwara, Takuya Kochi, and Fumitoshi Kakiuchi
  • Journal Title: Organic Letters Volume: 13巻 Pages: 3928-3931
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Coversion of sp^3 C-O Bonds in Ethers to C-C Bonds Using Triarylboroxines (2011)
  • Author(s): 荻原陽平、河内卓彌、垣内史敏
  • Journal Title: Organic Letters Volume: 13 Issue: 12 Pages: 3254-3257
  • DOI: 10.1021/ol2012007
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Acylation of Arylpyridines with Acyl Chlorides via ortho-Selective C-H Bond Cleavage (2011)
  • Author(s): 河内卓彌、田澤葵、本田一起、垣内史敏
  • Journal Title: Chemistry Letters Volume: 40 Issue: 9 Pages: 1018-1020
  • DOI: 10.1246/cl.2011.1018
  • NAID: 10029522752
  • Peer Reviewed
• [Journal Article] Control of product selectivity by styrene additive in ruthenium-catalyzed C-H arylation (2010)
  • Author(s): Shun Hiroshima, Daiki Matsumura, Takuya Kochi, Fumitoshi Kakiuchi
  • Journal Title: Organic Letters Volume: 12 Pages: 5318-5321
  • Peer Reviewed
• [Journal Article] Room-temperature regioselective C-H/olefin coupling of aromatic ketones using an activated ruthenium catalyst with a carbonyl ligand and structural elucidation of key intermediates (2010)
  • Author(s): Fumitoshi Kakiuchi, Takuya Kochi, Eiichiro Mizushima, Shinji Murai
  • Journal Title: Journal of the American Chemical Society Volume: 132 Pages: 17741-17750
  • Peer Reviewed
• [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-ジエン類からの選択的五員環形成反応 (2012)
  • Author(s): 浜崎太郎、河内卓彌、青山由果、河崎純一、垣内史敏
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 横浜
  • Year and Date: 2012-03-26
• [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-ジエン類からの選択的五員環形成反応 (2012)
  • Author(s): 浜崎太郎、河内卓彌、青山由果、河崎純一、垣内史敏
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 横浜
  • Year and Date: 2012-03-26
• [Presentation] Chain-Walking Strategy for Synthesis of Small Organic Molecules : Palladium-Catalyzed Formation of Five-Membered Rings from 1,n-Dienes (2011)
  • Author(s): Takuya Kochi, Taro Hamasaki, Yuka Aoyama, Junichi Kawasaki, Fumitoshi Kakiuchi
  • Organizer: The 10th International Symposium on Organic Reactions (ISOR10)
  • Place of Presentation: 横浜
  • Year and Date: 2011-11-24
• [Presentation] Chain-Walking Strategy for Synthesis of Small Organic Molecules : Palladium-Catalyzed Formation of Five-Membered Rings from 1, n-Dienes (2011)
  • Author(s): Takuya Kochi, Taro Hamasaki, Yuka Aoyama, Junichi Kawasaki, and Fumitoshi Kakiuchi
  • Organizer: The 10th International Symposium on Organic Reactions(ISOR10)
  • Place of Presentation: 横浜
  • Year and Date: 2011-11-23
• [Presentation] Ruthenium-Catalyzed Arylation of sp^3 C-O Bonds in Alkyl Ethers with Triarylboroxines via Dehydroalkoxylation (2011)
  • Author(s): Yohei Ogiwara, Takuya Kochi, and Fumitoshi Kakiuchi
  • Organizer: The 10th International Symposium on Organic Reactions(ISOR10)
  • Place of Presentation: 横浜
  • Year and Date: 2011-11-23
• [Presentation] Ruthenium-Catalyzed Arylation of sp^3 C-O Bonds in Alkyl Ethers with Triarylboroxines via Dehydroalkoxylation (2011)
  • Author(s): Yohei Ogiwara, Takuya Kochi, Fumitoshi Kakiuchi
  • Organizer: The 10th International Symposium on Organic Reactions (ISOR10)
  • Place of Presentation: 横浜
  • Year and Date: 2011-11-23
• [Presentation] チェーンウォーキングを経る1, n-ジエンの触媒的環化異性化反応 (2011)
  • Author(s): 河内卓彌、濱崎太郎、青山由果、河崎純一、垣内史敏
  • Organizer: 第100回有機合成シンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2011-11-10
• [Presentation] チェーンウォーキングを経る1,n-ジエンの触媒的環化異性化反応 (2011)
  • Author(s): 河内卓彌、濱崎太郎、青山由果、河崎純一、垣内史敏
  • Organizer: 第100回有機合成シンポジウム
  • Place of Presentation: 東京
  • Year and Date: 2011-11-10
• [Presentation] パラジウム触媒によるチェーンウォーキングを経る1, n-ジエン類の環化異性化反応 (2011)
  • Author(s): 濱崎太郎、青山由果、河崎純一、垣内史敏、河内卓彌
  • Organizer: 第58回有機金属化学討論会
  • Place of Presentation: 名古屋
  • Year and Date: 2011-09-09
• [Presentation] パラジウム触媒によるチェーンウォーキングを経る1,n-ジエン類の環化異性化反応 (2011)
  • Author(s): 濱崎太郎、青山由果、河崎純一、垣内史敏、河内卓彌
  • Organizer: 第58回有機金属化学討論会
  • Place of Presentation: 名古屋
  • Year and Date: 2011-09-09
• [Presentation] Palladium-Catalyzed Cycloisomerization of 1, n-Dienes via Chain-Walking (2011)
  • Author(s): Takuya Kochi, Taro Hamasaki, Yuka Aoyama, Junichi Kawasaki, and Fumitoshi Kakiuchi
  • Organizer: The 242th ACS National Meeting
  • Place of Presentation: Denver、CO、USA
  • Year and Date: 2011-08-30
• [Presentation] Palladium-Catalyzed Cycloisomerization of 1,n-Dienes via Chain-Walking (2011)
  • Author(s): Takuya Kochi, Taro Hamasaki, Yuka Aoyama, Junichi Kawasaki, Fumitoshi Kakiuchi
  • Organizer: The 242th ACS National Meeting
  • Place of Presentation: Denver, CO, USA
  • Year and Date: 2011-08-30
• [Presentation] Ruthenium-Catalyzed Arylation of sp^3 C-O Bonds in Alkyl Ethers (2011)
  • Author(s): Takuya Kochi, Yohei Ogiwara, and Fumitoshi Kakiuchi
  • Organizer: The 242th ACS National Meeting
  • Place of Presentation: Denver、CO、USA
  • Year and Date: 2011-08-29
• [Presentation] Ruthenium-Catalyzed Arylation of sp^3 C-O Bonds in Alkyl Ethers (2011)
  • Author(s): Takuya Kochi, Yohei Ogiwara, Fumitoshi Kakiuchi
  • Organizer: The 242th ACS National Meeting
  • Place of Presentation: Denver, CO, USA
  • Year and Date: 2011-08-29
• [Presentation] Ruthenium-Catalyzed C. C Bond Formation at sp^3 C. O Bonds in Ethers Using Arylboroxines (2011)
  • Author(s): Yohei Ogiwara, Takuya Kochi, and Fumitoshi Kakiuchi
  • Organizer: The 16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis(OMCOS 16)
  • Place of Presentation: Shanghai、China
  • Year and Date: 2011-07-25
• [Presentation] Ruthenium-Catalyzed C-C Bond Formation at sp^3 C-O Bonds in Ethers Using Arylboroxines (2011)
  • Author(s): Yohei Ogiwara, Takuya Kochi, Fumitoshi Kakiuchi
  • Organizer: The 16th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 16)
  • Place of Presentation: Shanghai, China
  • Year and Date: 2011-07-25
• [Presentation] 遷移金属触媒による芳香族炭素-水素結合切断を用いた革新的極性官能基導入法の開発 (2011)
  • Author(s): 河内卓彌
  • Organizer: 若い世代の特別講演会(日本化学会第91春季年会)
  • Place of Presentation: 横浜
  • Year and Date: 2011-03-28
• [Presentation] Chain-Walking Strategy for Synthesis of Cyclic Organic Molecules : Palladium-Catalyzed Cycloisomerization of 1,n-Dienes (2010)
  • Author(s): Takuya Kochi, Yuka Aoyama, Junichi Kawasaki, Taro Hamasaki, Fumitoshi Kakiuchi
  • Organizer: The 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: ホノルル、アメリカ合衆国
  • Year and Date: 2010-12-19