炭素ー水素結合変換による統合的合成化学の開拓

• Project/Area Number: 21675002
• Research Category: Grant-in-Aid for Young Scientists (S)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Nagoya University
• Principal Investigator: 伊丹 健一郎 Nagoya University, 理学(系)研究科(研究院), 教授 (80311728)
• Project Period (FY): 2009 – 2010
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥68,250,000 (Direct Cost: ¥52,500,000、Indirect Cost: ¥15,750,000); Fiscal Year 2011: ¥18,720,000 (Direct Cost: ¥14,400,000、Indirect Cost: ¥4,320,000); Fiscal Year 2010: ¥18,720,000 (Direct Cost: ¥14,400,000、Indirect Cost: ¥4,320,000); Fiscal Year 2009: ¥30,810,000 (Direct Cost: ¥23,700,000、Indirect Cost: ¥7,110,000)
• Keywords: 炭素水素結合変換 / 新反応 / 新触媒 / 機能性有機材料 / 医農薬 / カーボンナノチューブ / 天然有機化合物

Research Abstract

本研究では、「炭素-水素結合の直接化学変換」をキーワードにした分野横断型合成化学研究を、方法論に重点をおく2課題(新反応・新触媒開発、有機材料・医農薬合成)と標的物質に重点をおく2課題(カーボンナノチューブ合成、複雑天然物合成)によって推進する。各課題のH22年度の成果は以下の通りである。
(1) 新反応・新触媒開発 C-H結合変換に基づく芳香環連結を促進する新触媒の開発を行った。
チオフェンやチアゾールの直接アリール化において極めてユニークな位置選択性を有する2つの新規なパラジウム触媒を開発することに成功した。
(2) 有機材料・医農薬合成 前述した新規なパラジウム触媒反応を用いることで、Merck社から報告されているアルツハイマー病の治療薬のリード化合物であるSCH-785532(類縁体)の短工程合成法を確立することに成功した。
(3) カーボンナノチューブ合成 アームチェア型カーボンナノチューブの最短部分骨格であるシクロパラフェニレン(カーボンナノリング)の環サイズ選択的合成法および安価なニッケル錯体を用いた大量合成法の開発に成功した。また、シクロパラフェニレンのX線結晶構造解析に世界で初めて成功し、その特異な分子構造を明らかにした。
(4) 複雑天然物合成 インドールとピリジンN-オキシドのC-H/C-H直接連結反応を開発した。さらに開発した反応を用い、DNA結合活性を有する天然物Eudistomin Uの合成に成功した。

Research Products

• [Journal Article] Selective Introduction of Organic Groups to C60 and C70 Using Organoboron Compounds and Rhodium Catalyst : A New Synthetic Approach to Organo(hydro)fullerenes (2011)
  • Author(s): Masakazu Nambo, Yasutomo Segawa, Atsushi Wakamiya, Kenichiro Itami
  • Journal Title: Chem.Asian J. Volume: 6 Pages: 590-598
  • Peer Reviewed
• [Journal Article] Oxidative Biaryl Coupling of Thiophenes and Thiazoles with Arylboronic Acids through Palladium Catalysis : Otherwise-Difficult C4-Selective C-H Arylation Enabled by Boronic Acids (2011)
  • Author(s): Sylvia Kirchberg, Satoshi Tani, Kirika Ueda, Junichiro Yamaguchi, Armido Studer, Kenichiro Itami
  • Journal Title: Angew.Chem.Int.Ed. Volume: 50 Pages: 2387-2391
  • Peer Reviewed
• [Journal Article] Aziridinofullerene : A Versatile Platform for Functionalized Fullerenes (2011)
  • Author(s): Masakazu Nambo, Yasutomo Segawa, Kenichiro Itami
  • Journal Title: J.Am.Chem.Soc. Volume: 133 Pages: 2402-2405
  • Peer Reviewed
• [Journal Article] [9]Cycloparaphenylene : Nickel-Mediated Synthesis and Crystal Structure (2011)
  • Author(s): Yasutomo Segawa, Petr Senel, Sanae Matsuura, Haruka Omachi, Kenichiro Itami
  • Journal Title: Chem.Lett. Volume: 40 Pages: 423-425
  • NAID: 10028171020
  • Peer Reviewed
• [Journal Article] Oxidative C-H/C-H Coupling of Azine and Indole/Pyrrole Nuclei : Palladium Catalysis and Synthesis of Eudistomin U (2011)
  • Author(s): Atsushi D.Yamaguchi, Debashis Mandal, Junichiro Yamaguchi, Kenichiro Itami
  • Journal Title: Chem.Lett. Volume: 40 Pages: 555-557
  • NAID: 10028243360
  • Peer Reviewed
• [Journal Article] Photopatterning of Poly(arylene dienylene) by the Photoacid-Catalyzed Deprotection-Elimination Reaction of a Precursor Polymer (2010)
  • Author(s): Jean Bouffard, Mitsuru Watanabe, Hiroko Takaba, Kenichiro Itami
  • Journal Title: Macromolecules Volume: 43 Pages: 1425-1429
  • Peer Reviewed
• [Journal Article] Theoretical Studies on the Structures and Strain Energies of Cycloparaphenylenes (2010)
  • Author(s): Yasutomo Segawa, Haruka Omachi, Kenichiro Itami
  • Journal Title: Org.Lett. Volume: 12 Pages: 2262-2265
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed C-H Bond Arylation of Arenes (2010)
  • Author(s): Jean Bouffard, Kenichiro Itami
  • Journal Title: Topics in Current Chemistry (Volume : C-H Activation) ; Springer Volume: 292 Pages: 231-280
  • Peer Reviewed
• [Journal Article] A General Catalyst for the β-Selective C-H Bond Arylation of Thiophenes with Iodoarenes (2010)
  • Author(s): Kirika Ueda, Shuichi Yanagisawa, Junichiro Yamaguchi, Kenichiro Itami
  • Journal Title: Angew.Chem.Int.Ed. Volume: 49 Pages: 8946-8949
  • Peer Reviewed
• [Journal Article] Toward Ideal Arene Assembly : Catalytic C-H Bond Arylation of Aromatic Compounds (2010)
  • Author(s): Kenichiro Itami
  • Journal Title: J.Synth.Org.Chem., Jpn Volume: 68 Pages: 1132-1141
  • NAID: 10027371708
  • Peer Reviewed
• [Journal Article] A Modular and Size-Selective Synthesis of [n]Cycloparaphenylenes : A Step toward the Selective Synthesis of [n,n] Single-Walled Carbon Nanotubes (2010)
  • Author(s): Haruka Omachi, Sanae Matsuura, Yasutomo Segawa, Kenichiro Itami
  • Journal Title: Angew.Chem.Int.Ed. Volume: 49 Pages: 10202-10205
  • Peer Reviewed
• [Journal Article] Concise Synthesis and Crystal Structure of [12]Cycloparaphenylene (2010)
  • Author(s): Yasutomo Segawa, Shinpei Miyamoto, Haruka Omachi, Sanae Matsuura, Petr Senel, Takahiro Sasamori, Norihiro Tokitoh, Kenichiro Itami
  • Journal Title: Angew.Chem.Int.Ed. Volume: 50 Pages: 3244-3248
  • Peer Reviewed
• [Presentation] Challenges in Arene-Assembling Chemistry (2011)
  • Author(s): K.Itami
  • Organizer: The 5th Mitsui Chemicals International Symposium on Catalysis Science (MICS2011)
  • Place of Presentation: Chiba, Japan
• [Presentation] Challenges in Arene-Assembling Chemistry (2011)
  • Author(s): K.Itami
  • Organizer: The 1st International Conference on MEXT Project of Integrated Research on Chemical Synthesis
  • Place of Presentation: Sapporo, Japan
• [Presentation] C-H Bond Arylation of Arenes through Rh, Ir, Cu, Pd and Ni Catalysis (2010)
  • Author(s): K.Itami
  • Organizer: Pacifichem 2010 Symposium on C-H Functionalization
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 2010-12-19
• [Presentation] Cycloparaphenylenes : Synthesis, Structures, and Properties (2010)
  • Author(s): K.Itami
  • Organizer: The 10th IRTG Munster-Nagoya Joint Symposium
  • Place of Presentation: Munster, Germany
  • Year and Date: 2010-11-30
• [Presentation] Cycloparaphenylenes : Synthesis, Structures, and Properties (2010)
  • Author(s): K.Itami
  • Organizer: Hangzhou Symposium on Supramolecular Systems and Biomaterials
  • Place of Presentation: Zhejiang Univ, Hangzhou, China
  • Year and Date: 2010-10-31
• [Presentation] Challenges in Arene-Assembling Chemistry (2010)
  • Author(s): K.Itami
  • Organizer: The 20th Symposium on Optically Active Compounds
  • Place of Presentation: Tokyo, Japan
  • Year and Date: 2010-10-29
• [Presentation] Challenges in Arene-Assembling Chemistry (2010)
  • Author(s): K.Itami
  • Organizer: National Tsing Hua University Symposium
  • Place of Presentation: Taiwan
  • Year and Date: 2010-10-09
• [Presentation] Chemical Synthesis of Sidewall Segments of Carbon Nanotubes : Cycloparaphenylenes and Related Carbon Nanorings (2010)
  • Author(s): K.Itami
  • Organizer: The 93rd Canadian Chemistry Conference and Exhibition
  • Place of Presentation: Toronto, Canada
  • Year and Date: 2010-05-31
• [Presentation] Challenges in Arene-Assembling Chemistry (2010)
  • Author(s): K.Itami
  • Organizer: Special Lecture in Peking University
  • Place of Presentation: Beijin, China
  • Year and Date: 2010-04-09
• [Presentation] Challenges in Arene-Assembling Chemistry (2010)
  • Author(s): K.Itami
  • Organizer: Special Lecture in Wuhan University
  • Place of Presentation: Wuhan, China
  • Year and Date: 2010-04-08
• [Presentation] Challenges in Arene-Assembling Chemistry (2010)
  • Author(s): K.Itami
  • Organizer: Special Lecture in University of Science and Technology of China
  • Place of Presentation: Hefei, China
  • Year and Date: 2010-04-07
• [Presentation] Cycloparaphenylenes : Modular Synthesis, Crystal Structures, and Photophysical Properties (2010)
  • Author(s): K.Itami
  • Organizer: China-Japan Symposium on Catalytic Organic Synthesis
  • Place of Presentation: Nankai University, China
• [Presentation] Chemical Synthesis of Sidewall Segments of Carbon Nanotubes (2010)
  • Author(s): K.Itami
  • Organizer: China-Japan Joint Symposium on Functional Supramolecular Architectures
  • Place of Presentation: Jilin Univ, China
• [Presentation] Challenges in Arene-Assembling Chemistry (2010)
  • Author(s): K.Itami
  • Organizer: The 12th Belgian Organic Synthesis Symposium (BOSS-12)
  • Place of Presentation: University of Namur, Belgium
• [Presentation] Chemical Synthesis of Sidewall Segments of Carbon Nanotubes (2010)
  • Author(s): K.Itami
  • Organizer: The 6th Asian-European Symposium on Metal Mediated Efficient Reactions
  • Place of Presentation: Nanyang Technological University, Singapore