Development of Catalytic Transformations of Carbon-Carbon, Carbon-Oxygen and Carbon-Silicon Bonds

• Project/Area Number: 23685021
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Osaka University
• Principal Investigator: TOBISU Mamoru 大阪大学, 工学(系)研究科(研究院), 准教授 (60403143)
• Project Period (FY): 2011-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥28,990,000 (Direct Cost: ¥22,300,000、Indirect Cost: ¥6,690,000); Fiscal Year 2014: ¥5,850,000 (Direct Cost: ¥4,500,000、Indirect Cost: ¥1,350,000); Fiscal Year 2013: ¥5,850,000 (Direct Cost: ¥4,500,000、Indirect Cost: ¥1,350,000); Fiscal Year 2012: ¥5,850,000 (Direct Cost: ¥4,500,000、Indirect Cost: ¥1,350,000); Fiscal Year 2011: ¥11,440,000 (Direct Cost: ¥8,800,000、Indirect Cost: ¥2,640,000)
• Keywords: 均一系触媒 / 不活性結合活性化 / 炭素－酸素結合活性化 / 炭素－窒素結合活性化 / 炭素－リン結合活性化 / クロスカップリング / 炭素－炭素結合活性化 / 不活性結合切断

Outline of Final Research Achievements

Current synthetic methods depend on the ue of reactive chemical bonds. To change this situation, we have developed catalytic trasnformations of strong sigma bonds, in paricular those other than carbon-hydrogen bonds, which are the subject of intensive studies. Specific chemical bonds that we successfully used for catalytic transformations include carbon-carbon, carbon-oxygen, carbon-nitrogen, and carbon-phosphorus bonds. Through this study, we have expanded our own strategy for the activation of strong sigma bonds via the mechanism other than classical oxidative addition.

Research Products

• [Journal Article] Palladium-Catalyzed Synthesis of Six-Membered Benzofuzed Phosphacycles via Carbon-Phosphorus Bond Cleavage (2015)
  • Author(s): Katsuaki Baba, Mamoru Tobisu, and Naoto Chatani
  • Journal Title: Org. Lett. Volume: 17 Issue: 1 Pages: 70-73
  • DOI: 10.1021/ol503252t
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Rhodium-Catalyzed Borylation of Aryl and Alkenyl Pivalates through Cleavage of Carbon-Oxygen Bonds (2015)
  • Author(s): Hirotaka Kinuta, Junya Hasegawa, Mamoru Tobisu, Naoto Chatani
  • Journal Title: Chem. Lett. Volume: 44 Issue: 3 Pages: 366-368
  • DOI: 10.1246/cl.141084
  • NAID: 130004868406
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Rhodium-catalyzed Cross-Coupling of Aryl Carbamates with Arylboron Reagents (2015)
  • Author(s): K. Nakamura, K. Yasui, M. Tobisu, and N. Chatani
  • Journal Title: Tetrahedron Volume: 71 Issue: 26-27 Pages: 4484-4489
  • DOI: 10.1016/j.tet.2015.02.088
  • Peer Reviewed
• [Journal Article] Theoretical Studies of Rhodium-Catalyzed Borylation of Nitriles through Cleavage of Carbon-Cyano Bonds (2014)
  • Author(s): Hirotaka Kinuta, Hiroaki Takahashi, Mamoru Tobisu, Seiji Mori, and Naoto Chatani
  • Journal Title: Bull Chem Soc Jpn Volume: 87 Issue: 6 Pages: 655-669
  • DOI: 10.1246/bcsj.20130332
  • NAID: 130004059118
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Nickel-Catalyzed Reductive and Borylative Cleavage of Aromatic Carbon-Nitrogen Bonds in N-Aryl Amides and Carbamates (2014)
  • Author(s): M. Tobisu, K. Nakamura, and N. Chatani
  • Journal Title: J. Am. Chem. Soc. Volume: 136 Issue: 15 Pages: 5587-5590
  • DOI: 10.1021/ja501649a
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Palladium-Catalyzed Direct Synthesis of Phosphole Derivatives from Triarylphosphines via Cleavage of Carbon-Hydrogen and Carbon-Phosphorus Bonds (2013)
  • Author(s): Katsuaki Baba
  • Journal Title: Angewandte Chemie International Edition Volume: 52 Issue: 45 Pages: 11892-11895
  • DOI: 10.1002/anie.201307115
  • Peer Reviewed
• [Journal Article] 1,5-Migration of rhodium via C–H bond activation in catalytic decyanative silylation of nitriles (2012)
  • Author(s): Mamoru Tobisu, Junya Hasegawa, Yusuke Kita, Hirotaka Kinutab and Naoto Chatani
  • Journal Title: Chamical Communications Volume: 48 Issue: 93 Pages: 11437-11439
  • DOI: 10.1039/c2cc36601k
  • Peer Reviewed
• [Journal Article] Rhodium(I)-Catalyzed Borylation of Nitriles through the Cleavage of Carbon‒Cyano Bonds (2012)
  • Author(s): Tobisu, M.; Kinuta, H.; Kita, Y.; Rémond, E.; Chatani, N
  • Journal Title: J. Am. Chem. Soc Volume: 134 Issue: 1 Pages: 115-118
  • DOI: 10.1021/ja2095975
  • Peer Reviewed
• [Journal Article] Ni(0)/NHC-Catalyzed Amination of N-Heteroaryl Methyl Ethers through the Cleavage of Carbon-Oxygen Bonds (2012)
  • Author(s): Tobisu, M.; Yasutome, A.; Yamakawa, K.; Shimasaki, T.; Chatani, N.
  • Journal Title: Tetrahedron Volume: 68 Issue: 26 Pages: 5157-5161
  • DOI: 10.1016/j.tet.2012.04.005
  • Peer Reviewed
• [Journal Article] Novel Synthetic Approach to Arylboronates via Rhodium-Catalyzed Carbon-Cyano Bond Cleavage of Nitriles (2012)
  • Author(s): Kinuta, H.; Kita, Y.; Remond, E.; Tobisu, M.; Chatani, N.
  • Journal Title: Synthesis Volume: 44 Issue: 19 Pages: 2999-3002
  • DOI: 10.1055/s-0031-1290370
  • Peer Reviewed