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Synthesis and Application of Highly Coordinated Nitrogen-Ligands

Research Project

Project/Area Number 08455425
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionToyohashi University of Technology

Principal Investigator

NISHIYAMA Hisao  Toyohashi University of Technology, Faculty of Engineering, School of Materials Science, Professor, 工学部, 教授 (40135421)

Project Period (FY) 1996 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥7,100,000 (Direct Cost: ¥7,100,000)
Fiscal Year 1998: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1997: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1996: ¥3,900,000 (Direct Cost: ¥3,900,000)
Keywordsnitrogen ligand / optically active / asymmetric induction / stereo control / catalysis / 不斉合成 / ルテニウム / ミクロプロバン化 / エポキシ化 / オキサゾリン / ルテニウム錯体 / 立体選択性 / 酸化反応 / ピリジン系配位子 / 不斉エポキシ化 / ジアセトキシヨードベンゼン / オレフィン / 金属錯体
Research Abstract

1) Highly coordinated nitrogen-ligands were synthesized to be applied to asymmetric catalytic cylcopropanation of olefins with ruthenium catalysis. The intermediate carbene complexes were determined by NMR and X-ray analysis, and its geometry and moleculer orbitals were considered.
2) Single chiral version of nitrogen-ligand were discovered and applied to asymmetric cyclopropanation to give high enantioselectivity.
3) Chiral oxazoline ligand designed in this research exhibited high efficiency in asymmetric cylcopropanation over 80% ees.
4) New nitrogen-benzene ligands were developed for asymmetric catalysis. One of them exhibited high efficiency in asymmetric allylation of aldehydes, and the catalyst proved to be recovered for reuse.

Report

(4 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • 1996 Annual Research Report
  • Research Products

    (16 results)

All Other

All Publications (16 results)

  • [Publications] Y.Motoyama, et al: "Chiral Bis(oxazolinyl)phenylrodium(III)complexes as Levus Acid Catalysts" J.Chem.Soc., Chem.Commun.131-132 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Nishiyama, et al: "Single Chiral bis(oxazolinyl)pyridine Efficiency in Asymmetric catalytic cyclopropanation" Tetrahedron : Asymmetry. 9. 2865-2869 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Nishiyama: "Advances in Catalytic Processes, vol 2" JAI Press, 287 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Y.Motoyama, H.Narusawa, H.Nishiyama: "Chiral Bis (oxazolinyl) phenylrhodium (III) Complexes as Lewis Acid Catalysts for Enantioselective Allylation of Aldehydes" Chem.Commun.131-132 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Nishiyama, N.Sakata, H.Sugimoto, Y.Motoyama, H.Wakita, H.Nagase: "Synthesis of Optically Active Cyclopenta [b] benzofuran as a Precusor of m-Phenyleneprostacyclin" Synlett.930 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Nishiyama, N.Soeda, T.Naito, Y.Motoyama: "Single-chiral bis (oxazolinyl) pyridine (pybox). Efficiency in asymmetric catalytic cyclopropanation" Tetrahedron : Asymmetry. 9. 2865 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Motoyama.Y. ; Murata, K. ; Kurihara, O. ; Nitoh, T. ; Aoki, K. ; Nishiyama, H.: "Enantiofacially selective olefin coordination of alpha, beta-unsaturated carbonyl compounds to chiral bis (oxazolinyl) pyridineruthenium fragments" Organometallics. 17. 1251 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Nishiyama, H. ; Shimada, T. ; Itoh, H. ; Sugiyama, H. ; Motoyama, Y: "Novel rethenium-pyridinecarboxylate complexes of terpyridine and chiral bis (oxazolinyl) pyridine : a new catalytic system for alkene epoxidation with [bis (acetoxyl) iodo] benzene as an oxygene donor" J.Chem.Soc., Chem.Commun.1863 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Motoyama Y. ; Makihara, N. ; Mikami, Y. ; Aoki, K. ; Nishiyama.H.: "Chiral Bis (oxazolinyl) phenyl Rhodium and Palladium Complexes" Chem.Lett.951 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Mizushima, K. ; Nakaura, M. ; Park, S.-B. ; H.Nishiyama ; Monjushiro, H. ; Harada, K. ; Haga, M.: "Ruthenium (II) complexes with the terdentate 6,6'-bis (oxazolinyl or benzimidazolyl)-2,2'-bipyridine ligand : syntehsis, electrochemixal properties, and catalytic reactivities" Inorg, Chim.Acta. 261. 175 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Doyle, M.P ; Peterson, C.S. ; Zhou, Q.-L. ; Nishiyama.H.: "Comparative evaluation of enantioscontrol for intramolecular cyclopropanation of diazoacetates with chiral Cu (I), Rh (II) and Ru (II) catalysts" J.Chem.Soc., Chem.Commun. 211 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Park, S.B. ; Sakata, N. ; Nishiyama, H.: "Aryloxylcarbonylcarbene Complexses of Bis (oxazolinyl) pyridineruthenium as Active Intermediates in Asymmetric Catalytic Cyclopropanation" Chem.Eur.J.2. 303-306 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hisao Nishiyama: Chiral Bis (oxazolin-yl) pyridine (PYBOX) Ligands for Asymmetric Transition Metal Catalysis, in "Advances in Catalytic Processes. Vol2". ed by M.P.Doyle ; JAI Press Inc. (New York)., 153-188 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Y.Motoyama, H.Nishiyama: "Chiral Bis(Oxazolinyl)phenylrodium(III)Complexes as Lounis Acid Catalysts" J.Chem.Soc.,Chem Comm.(in press). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Hisao Nishiyama: "Advances in Catalytic Process Vol2. P153-188" JAI Press Inc(Now York),Ed M.P.Doyle, 35(287) (1997)

    • Related Report
      1998 Annual Research Report
  • [Publications] Y.Motoyama, H.Nishiyama その他: "driral Bis (cxazlinyl) phenyl Ruthenium and Palladium Compleroes" Chem.Lett.951-952 (1997)

    • Related Report
      1997 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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