Development of Activation of Unreactive Bonds and its Application to Catalytic Reactions

• Project/Area Number: 18205013
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Synthetic chemistry
• Research Institution: Osaka University
• Principal Investigator: CHATANI Naoto Osaka University, 大学院・工学研究科, 教授 (30171953)
• Co-Investigator(Kenkyū-buntansha): TOBISU Mamoru 大阪大学, 大学院・工学研究科グローバル若手フロンティア研究拠点, 特任講師 (60403143)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥40,820,000 (Direct Cost: ¥31,400,000、Indirect Cost: ¥9,420,000); 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: 炭素不活性結合 / 炭素-水素結合活性化 / 炭素-酸素結合活性化 / 炭素-炭素結合活性化 / カルボニル化 / クロスカップリング / シリル化 / 二座配向基 / 芳香族アミド / 脱シアノ化 / 芳香族ニトリル / エンイン / 骨格再配列 / ロジウム / フェニルピリジン / キレーション / 一酸化炭素 / アミノ化

Research Abstract

キレーションを利用する炭素-水素結合の活性化は今では有機合成化学の一般的手法となっている。しかし、そのほとんどは単座の配向基を利用したものであった。二座配向基を用いることで炭素-水素結合の新しい形式のカルボニル化反応の開発に成功した。ロジウム/ケイ素試薬系で炭素-シアノ結合のシリル化、還元反応、環化反応、Mizoroki-Heck型反応の開発にも成功した。さらに、アニソール誘導体のSuzuki-Miyaura型カップリングがニッケル触媒存在下、進行することも見出した。

Research Products

• [Journal Article] Rhodium-Catalyzed Coupling of 2-Silylphenylboronic Acids with Alkynes Leading to Benzosiloles (2009)
  • Author(s): M. Tobisu, M. Onoe, Y. Kita, N. Chatani, J. Am. Chem. Soc., J. Am. Chem. Soc.
  • Journal Title: Catalytic Cleavage of the Carbon-Silicon Bond in Trialkylsilyl Groups 131(22) Pages: 7506-7507
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Carbonylation at ortho C-H Bonds in Aromatic Amides Leading to Phthalimides (2009)
  • Author(s): S. Inoue, H. Shiota, Y. Fukumoto, N. Chatani, J. Am. Chem. Soc.
  • Journal Title: C-H Bond Activation Utilizing a Bidentate System 131(20) Pages: 6898-6899
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Reductive Cleavage of Carbon-Cyano Bonds with Hydrosilanes (2009)
  • Author(s): M. Tobisu, R. Nakamura, Y. Kita, N. Chatani, J. Am. Chem. Soc
  • Journal Title: A Catalytic Protocol for Removal of Cyano Groups 131(9) Pages: 3174-3175
  • Peer Reviewed
• [Journal Article] Unique Effect of Coordination of an Alkene Moiety in Products on Ruthenium-Catalyzed Chemoselective C-H Alkenylation (2009)
  • Author(s): S. Ueno, T. Kochi, N. Chatani, F. Kakiuchi
  • Journal Title: Org. Lett. 11(4) Pages: 855-858
  • Peer Reviewed
• [Journal Article] Rhodium-Catalysed Anomalous Dimerization of Styrenes Involving the Cleavage of the ortho C-H Bond (2009)
  • Author(s): N.Chatani
  • Journal Title: Chem.Commun. Pages: 6013-6015
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Reductive Cleavage of Carbon-Cyano Bonds with Hydrosilanes : A Catalytic Protocol for Removal of Cyano Groups (2009)
  • Author(s): N.Chatani
  • Journal Title: J.Am.Chem.Soc 131 Pages: 3174-3175
  • Peer Reviewed
• [Journal Article] Rhodium-Catalysed Anomalous Dimerization of Styrenes Involving the Cleavage of the ortho C-H Bond (2008)
  • Author(s): M. Tobisu, I. Hyodo, M. Onoe, N. Chatani
  • Journal Title: Chem. Commun. (45) Pages: 6013-6015
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Silylation and Intramolecular Arylation of Nitriles via the Silicon-Assisted Cleavage of Carbon-Cyano Bonds (2008)
  • Author(s): M. Tobisu, Y. Kita, Y. Ano, N. Chatani
  • Journal Title: J. Am. Chem. Soc. 130(47) Pages: 15982-15989
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Silylation of Aromatic Carbon-Hydrogen Bonds in 2-Arylpyridines Using Disilane (2008)
  • Author(s): M. Tobisu, Y. Ano, N. Chatani
  • Journal Title: Chem. Asian J. 3(8) Pages: 1585-1591
  • Peer Reviewed
• [Journal Article] Rh(I)-Catalyzed Reaction of 2-(Chloromethyl)-phenylboronic Acids and Alkynes Leading to Indenes (2008)
  • Author(s): M. Miyamoto, Y. Harada, M. Tobisu, N. Chatani
  • Journal Title: Org. Lett. 10(14) Pages: 2975-2978
  • Peer Reviewed
• [Journal Article] Rh(II)-Catalyzed Skeletal Reorganization of Enynes Involving Selective Cleavage of C-C Triple Bonds (2008)
  • Author(s): K. Ota, N. Chatani
  • Journal Title: Chem. Commun. (25) Pages: 2906-2907
  • Peer Reviewed
• [Journal Article] Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers with Aryl Boronic Esters (2008)
  • Author(s): M. Tobisu, T. Shimasaki, N. Chatani
  • Journal Title: Angew. Chem., Int. Ed. 47(26) Pages: 4866-4869
  • Peer Reviewed
• [Journal Article] Rhodium-Catalyzed Silylation and Intramolecular Arylation of Nitrilesvia the Silicon-Assisted Cleavage of Carbon-Cyano Bonds (2008)
  • Author(s): N.Chatani
  • Journal Title: J.Am.Chem.Soc 130 Pages: 15982-15989
  • Peer Reviewed
• [Journal Article] A Chelation-Assisted Transformation: Synthesis of Maleimides by the Rh-Catalyzed Carbonylation of Alkynes with Pyridin-2-ylmethylamine (2008)
  • Author(s): N. Chatani
  • Journal Title: Chemical Society Review 37 Pages: 300-307
  • Peer Reviewed
• [Journal Article] 2H-and 13C-Labelling Studies on Sketal Reorganization of 1, 6-Enynes (2007)
  • Author(s): H. Nakai, d N. Chatani
  • Journal Title: Chem. Lett. 36(12) Pages: 1494-1495
  • Peer Reviewed
• [Journal Article] A Chelation-Assisted Transformation: Synthesis of Maleimides by the Rh-Catalyzed Carbonylation of Alkynes with Pyridin-2-ylmethylamine (2007)
  • Author(s): S. Inoue, Y. Fukumoto, N. Chatani
  • Journal Title: J. Org. Chem. 72(17) Pages: 6588-6590
  • Peer Reviewed
• [Journal Article] Lewis Acid-Promoted Imine Synthesis by the Insertion of Isocyanides into C-H Bonds of Electron-Ricj Aromatic Compounds (2007)
  • Author(s): M. Tobisu, S. Yamaguchi, N. Chatani
  • Journal Title: Org. Lett. 9(17) Pages: 3351-3353
  • Peer Reviewed
• [Journal Article] The Ru(cod)(cot)-Catalyzed Alkenylation of Aromatic C-H Bonds with Alkenyl Acetates (2007)
  • Author(s): Y. Matsuura, M. Tamura, T. Kochi, M. Sato, N. Chatani, F. Kakiuchi
  • Journal Title: J. Am. Chem. Soc. 129(32) Pages: 9858-9859
  • Peer Reviewed
• [Journal Article] Ruthenium-Catalyzed Carbon-Carbon Bond Formation via the Cleavage of an Unreactive Aryl Carbon-Nitrogen Bond in Aniline Derivatives with Organoboronates (2007)
  • Author(s): S. Ueno, N. Chatani, F. Kakiuchi
  • Journal Title: J. Am. Chem. Soc. 129(19) Pages: 6098-6099
  • Peer Reviewed
• [Journal Article] Regioselective Alkenylation of Aromatic Ketones with Alkenylboronates Using a RuH2(CO)(PPh3)3-Catalyst via Carbon-Hydrogen Bond Cleavage (2007)
  • Author(s): S. Ueno, N. Chatani, F. Kakiuchi
  • Journal Title: J. Org. Chem. 72(9) Pages: 3600-3602
  • Peer Reviewed
• [Journal Article] Ru/C-Catalyzed Carbonylation at ortho C-H Bonds in 2-Phenylpyridines (2007)
  • Author(s): S. Imoto, T. Uemura, F. Kakiuchi, N. Chatani
  • Journal Title: Synlett (1) Pages: 170-172
  • Peer Reviewed
• [Journal Article] ^2H- and ^<13>C-Labelling Studies on Sketal Reorganization f 1, 6-Enynes (2007)
  • Author(s): N. Chatani
  • Journal Title: Chemistry Letters 37 Pages: 1494-1495
  • Peer Reviewed
• [Journal Article] A Chelation-Assisted Transformation: Synthesis of Maleimides by the Rh-Catalyzed Carbonylation of Alkynes with Pyridin-2-ylmethylamine (2007)
  • Author(s): N. Chatani
  • Journal Title: The Journal of Organic Chemistry 72 Pages: 6588-6590
  • Peer Reviewed
• [Journal Article] Ru/C-Catalyzed Carbonylation at ortho C-H Bonds in 2-Phenylpyridines (2007)
  • Author(s): N. Chatani
  • Journal Title: Synlett (1) Pages: 170-172
• [Journal Article] Direct Observation of the Oxidative Addition of the Aryl Carbon-Oxygen Bond to a Ruthenium Complex and Consideration of the Relative Reactivity between Aryl Carbon-Oxygen and Aryl Carbon-Hydrogen Bonds (2006)
  • Author(s): S. Ueno, E. Mizushima, N. Chatani, F. Kakiuchi
  • Journal Title: J. Am. Chem. Soc. 128(51) Pages: 16516-16517
  • Peer Reviewed
• [Journal Article] Synthesis of [Ru(CO)2(PPh3)(SP)] and [Ru(CO)(PPh3)2(SP)] and Their Catalytic Activities for the Hydroamination of Phenylacetylene (2006)
  • Author(s): E. Mizushima, N. Chatani, F. Kakiuchi
  • Journal Title: J. Organomet. Chem. 691(26) Pages: 5751-5757
  • Peer Reviewed
• [Journal Article] Amination of the ortho C-H Bonds by the Cu(OAc)2-Mediated Reaction of 2-Phenylpyridines with Anilines (2006)
  • Author(s): T. Uemura, S. Imoto, N. Chatani
  • Journal Title: Chem. Lett. 35(8) Pages: 842-843
  • Peer Reviewed
• [Journal Article] Rh(I)-Catalyzed Silylation of Aryl and Alkenyl Cyanides Involving the Cleavage of C-C and Si-Si Bonds (2006)
  • Author(s): M. Tobisu, Y. Kita, N. Chatani
  • Journal Title: J. Am. Chem. Soc. 128(25) Pages: 8152-8153
  • Peer Reviewed
• [Journal Article] A Chelation-Assisted Transformation: Synthesis of 1, 4-Dicarboxylate Esters by the Rh-Catalyzed Carbonylation of Internal Alkynes with 2-Pyridinylmethanol (2006)
  • Author(s): S. Inoue, K. Yokota, H. Tatamidani, Y. Fukumoto, N. Chatani
  • Journal Title: Org. Lett. 8(12) Pages: 2519-2522
  • Peer Reviewed
• [Journal Article] A Chelation-Assisted Transformation: Synthesis of 1,4-Dicarboxylate Esters by the Rh-Catalyzed Carbonylation of Internal Alkynes with 2-Pyridinylmethanol (2006)
  • Author(s): N. Chatani
  • Journal Title: Organic Letters 8(12) Pages: 2519-2522
• [Journal Article] Rh(I)-Catalyzed Silylation of Aryl and Alkenyl Cyanides Involving the Cleavage of C-C and Si-Si Bonds (2006)
  • Author(s): N. Chatani
  • Journal Title: Journal of the American Chemical Society 128(25) Pages: 8152-8153
• [Journal Article] Amination of the ortho C-H Bonds by the Cu (OAc)_2-Mediated Reaction of 2-Phenylpyridines with Anilines (2006)
  • Author(s): N. Chatani
  • Journal Title: Chemistry Letters 35(8) Pages: 842-843
  • NAID: 10018187232
• [Presentation] Nickel-Catalyzed Cross-Coupling of Aryl Methyl Ethers with Aryl Boronic Esters (2008)
  • Author(s): N. Chatani
  • Organizer: 23th International Conference on Organometallic Chemistry 2008 (ICOMC 2008)
  • Place of Presentation: フランスレンヌ
  • Year and Date: 2008-07-17
• [Presentation] Chelation-Assisted Transformations: C-H Bond Silylation and Carbonylation (2008)
  • Author(s): N. Chatani
  • Organizer: Osaka University Forum 2008
  • Place of Presentation: San Francisco, USA
• [Presentation] Nickel-Catalyzed Miyaura- Suzuki Type Coupling Reaction of Anisoles (2008)
  • Author(s): N. Chatani
  • Organizer: International Symposium on Advanced Green Catalysis and Materials (Pre-ISOR)
  • Place of Presentation: Taipei, Taiwan
• [Presentation] Rh(I)-Catalyzed Reactions of Alkynes with Halo-Substituted Phenylboronic Acids (2008)
  • Author(s): Harada, J. Nakanishi, M. Miyamoto, N. Chatani
  • Organizer: Strasbourg-Osaka Joint Symposium
  • Place of Presentation: Osaka, Japan
• [Presentation] Skeletal Reorganization of Enynes Involving Cleavage of C-C Triple Bonds (2008)
  • Author(s): N. Chatani
  • Organizer: 5th Asian-European Symposium on Metal- Mediated Efficient Organic Synthesis
  • Place of Presentation: Obernai, France
• [Presentation] (2008)
  • Author(s): N. Chatani
  • Organizer: The 4th Kansai-CMDS Meeting on OMCOS
  • Place of Presentation: Gyungiu, Korea
• [Presentation] Chelation-Assisted Transformations : C-H Bond Silylation and Carbonylation (2008)
  • Author(s): N.Chatani
  • Organizer: Osaka University Forum 2008
  • Place of Presentation: San Francisco, USA
• [Presentation] Catalytic Transformations of C-H Bonds (2007)
  • Author(s): N. Chatani
  • Organizer: Japan-England Green Chemistry Symposium
  • Place of Presentation: Suita, Japan
  • Year and Date: 2007-03-27
• [Presentation] Rh(I)-Catalyzed Carbonylative Cyclization Reactions of Alkynes with 2-Bromophenylboronic Acids Leading to Indenones (2007)
  • Author(s): N. Chatani
  • Organizer: 2nd Aachen-Osaka Joint Symposium
  • Place of Presentation: Osaka
• [Presentation] Rh(I)-Catalyzed Carbonylative Cyclization Reactions of Alkynes with 2-Bromophenylboronic Acids Leading to Indenones (2007)
  • Author(s): N. Chatani
  • Organizer: The 13th Korea-Japan Seminar on Organic Chemistry
  • Place of Presentation: Daejeon, Korea
• [Presentation] Rh(I)- Catalyzed Silylation of Aryl and Alkenyl Cyanides Involving the Cleavage of C-C and Si-Si Bonds (2006)
  • Author(s): M. Tobisu, Y. Kita, N. Chatani
  • Organizer: 4th Spanish-Portuguess-Japanese Organic Chemistry Symposium (SPJ-OCS), Santiago de Compostela
  • Place of Presentation: Spain
• [Presentation] Catalytic Skeletal Reorganization of Enynes (2006)
  • Author(s): N. Chatani
  • Organizer: 7th Tetrahedron Symposium
  • Place of Presentation: Kyoto, Japan
• [Presentation] (2006)
  • Author(s): N. Chatani
  • Organizer: The 3rd CMDS-Kansai Meeting on OMCOS
  • Place of Presentation: Yamashiro, Japan
• [Book] Directed Metallation In Topics in Organometallic Chemistry (2007)
  • Author(s): Naoto Chatani (Volume Editor)
  • Publisher: Springer-Verlag
• [Book] Directed Metallation In Topics in Organometallic Chemistry (2007)
  • Author(s): N. Chatani(volume editor)
  • Total Pages: 206
  • Publisher: Springer
• [Remarks]
  • URL: http://www.chem.eng.osaka-u.ac.jp/~chatani-lab/