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2003 Fiscal Year Final Research Report Summary

Novel Catalytic Organic Synthesis via Ruthenium-Heteroatom Bond Formation

Research Project

Project/Area Number 13450363
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 有機工業化学
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

MITSUDO Takeaki  Kyoto Univ., Graduate School of Eng., Professor, 工学研究科, 教授 (90026344)

Co-Investigator(Kenkyū-buntansha) URA Yasuyuki  Kyoto Univ., Graduate School of Eng., Instructor, 工学研究科, 助手 (40335196)
WADA Kenji  Kyoto Univ., Graduate School of Eng., Lecturer, 工学研究科, 講師 (10243049)
KONDO Teruyuki  Kyoto Univ., Graduate School of Eng., Associate Professor, 工学研究科, 助教授 (20211914)
Project Period (FY) 2001 – 2003
KeywordsRuthenium catalyst / Propargylation / Thiol / Sulfenamide / Alkyne / η^6-Arene complex / ρ-Quinone complex / キノン錯体
Research Abstract

The formation of metal-heteroatom bond formation is important as a key step for developing novel catalytic heterofunctionalization of unsaturated compounds. In this study, we paid our attention to the formation of ruthenium-hetero atom bond, and the following novel ruthenium-catalyzed reactions have been developed. First, we found that low-valent ruthenium complexes with a π-acidic ligand, such as Ru(η^6-cot)(dmfm)_2 [cot = 1,3,5-cyclooctatriene, dmfm = dimethyl fumarate] and Ru_3(CO)_<12>, are highly active catalysts for the intramolecular hydroamination of aminoalkynes. The reaction is highly regioselective, and a nitrogen atom is selectively attached to an internal carbon of alkynes to give five-, six-, and seven-membered nitrogen heterocycles as well as indoles in good to high yields. Second, we showed that [RuCl_2(CO)_3]_2ldppp [dppp = 1,3-bis(diphenylphosphino)propane] was a highly effective catalyst system for the first intramolecular oxidative amination of a variety of aminoalk … More enes when it was used concomitantly with K_2CO_3 and allyl acetate in N-methylpiperidine, to give the corresponding cyclic imines and indoles in excellent yields. Futhermore, a new and highly efficient catalytic system based on CpRuClL_2 is proposed for the S-propargylation of thiols by propargyl carbonates under neutral conditions, in which specific requirements inherent to the different reactivities of aliphatic and aromatic thiols are achieved by tuning both the nature of thee ancillary ligand L and experimental conditions.. On the other hand, sulfenamides smoothly add to electron-deficient alkynes by [RuCl_2(CO)_3]_2 or Ru_3(CO)_<12> catalyst to give the corresponding polyfunctional alkenes in high yield with high regio-and stereoselectivity (Z 100%).
Recently, we have also reported the novel zerovalent ruthenium complex Ru(η_6-cot)(dmfm)2, which showed high catalytic activity in a unique dimerization of 2,5 norbornadiene to novel half-cage compounds, PCTD [pentacyclo[6.6.0.0^<2,6> 0^<3,13> 0^<10,14>]tetradeca-4,11-diene]. During our further investigation of the reactivity of this complex, we found that the reaction with p-quinones gave Ru(η^6-cot)(ρ-quinone) complexes and the reaction with arenes gave novel (η6-arene)Ru(dmfm)2 complex, as well as the formation of Ru(dmfm)2(N-N'-N") complexes by the reactions with tridentate pyridyl ligands such as 2,2':6',2"-terpyridine (N-N'-N"). All reactions proceeded via the direct ligand exchange reactions of cot andlor dmfm in Ru(η^6-cot)(dmfm)_2, and the new complexes prepared here can be expected as efficient catalysts for heterofunctionalization of unsaturated compounds. Less

  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] Teruyuki Kondo: "Ruthenium-Catalyzed Intramolecular Hydroamination of Aminoalkynes"Journal of Organometallic Chemistry. 622・1-2. 149-154 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Teruyuki Kondo: "Ruthenium-Catalyzed Intramolecular Oxidative Amination of Aminoalkenes Enables Rapid Synthesis of Cyclic Imines"Journal of the American Chemical Society. 124・2. 186-187 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Teruyuki Kondo: "Ruthenium-Catalyzed S-Propargylation of Thiols Enables the Rapid Synthesis of Propargyl Sulfides"Journal of the American Chemical Society. 124・44. 12960-12961 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Masashi Shiotsuki: "Synthesis, Structure, and Reactivity of a Stable Zerovalent Ruthenium Aqua Complex"Organometallics. 21・23. 4960-4964 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Masashi Shiotsuki: "Synthesis and Structure of Novel Zerovalent Ruthenium Complexes with Three Pyridine Ligands or Tridentate Pyridyl Ligands"Organometallics. 22・6. 1332-1339 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yasuyuki Ura: "Synthesis of Novel Zerovalent Ruthenium η^6-Arene Complexes via Direct Displacement of a 1,3,5-Cyclooctatriene Ligand by Arenes"Organometallics. 22・9. 1863-1867 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Teruyuki Kondo, Takumi Okada, Toshiaki Suzuki, Take-aki Mitsudo: "Ruthenium-Catalyzed Intramolecular Hydroamination of Aminoalkynes"Journal of Organometallic Chemistry. Vol.-622, No. 1-2. pp149-pp154 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Teruyuki Kondo, Takumi Okada, Take-aki Mitsudo: "Ruthenium-Catalyzed Intramolecular Oxidative Amination of Aminoalkenes Enables Rapid Synthesis of Cyclic Imines"Journal of the American Chemical Society. Vol. 124, No. 2. pp186-pp187 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Teruyuki Kondo, Yusuke Kanda, Atsushi Baba, Kenji Fukuda, Ayako Nakamura, Kenji Wada, Yasuhiro Morisaki, Take-aki Mitsudo: "Ruthenium-Catalyzed S-Propargylation of Thiols Enables the Rapid Synthesis of Propargyl Sulfides"Journal of the American Chemical Society. Vol. 124, No. 2. pp12960-pp12961 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Masashi Shiotsuki, Hiroshi Miyai, Yasuyuki Ura, Toshiaki Suzuki, Teruyuki Kondo, Take-aki Mitsudo: "Synthesis, Structure, and Reactivity of a Stable Zerovalent Ruthenium Aqua Complex"Organometallics. Vol.21, No.23. pp4960-pp4964 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Masashi Shiotsuki, Toshiaki Suzuki, Kazuo Iida, Yasuyuki Ura, Kenji Wada, Teruyuki Kondo, Take-aki Mitsudo: "Synthesis and Structure of Novel Zerovalent Ruthenium Complexes with Three Pyridine Ligands or Tridentate Pyridyl Ligands"Organometallics. Vol. 22, No. 6. pp1332-pp1339 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yasuyuki Ura, Masashi Shiotsuki, Kazuo Sadaoka, Toshiaki Suzuki, Teruyuki Kondo, Take-aki Mitsudo: "Synthesis of Novel Zerovalent Ruthenium η^6-Arene Complexes via Direct Displacement of a 1,3,5-Cyclooctatriene Ligand by Arenes"Organometallics. Vol. 22, No. 9. pp1863-pp1867 (2003)

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      「研究成果報告書概要(欧文)」より

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Published: 2005-04-19  

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