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1996 Fiscal Year Final Research Report Summary

HIGHLY SELECTIVE CARBON BOND FORMING REASTIONS BY MEANS OF DESIGNED LIGAND FIELDS OF RUTHENIUM

Research Project

Project/Area Number 06453134
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionNAGOYA UNIVERSITY (1995-1996)
Toyohashi University of Technology (1994)

Principal Investigator

ITOH Kenji  NAGOYA UNIVERSITY FACULTY OF ENGINEERING,DEPARTMENT OF APPLITED CHEMISTRY,PROFESSOR, 工学部, 教授 (60023149)

Project Period (FY) 1994 – 1996
KeywordsOligomerization of dienes / Cyclopropanation / Asymmetric synthesis / Ruthenium catalysis / Complex catalyst / Carbene complex / Metathesis / Cycloaddition
Research Abstract

(1) The cationic species derived from (C_5M_<e5>) RuCl (diene) and silver ion was founde to be highly selective catalysts for [4+4] cyclodimerization of butadiene or isoprene. The structure of an intermediate 1,3,7-octatriene complex was determined unequivocally by single crystal X-ray analysis. In the case of 1,3-pentadiene, regioselective linear dimerization of the diene took place by way of a bis (pi-allylic) ruthenium (IV) intermediate which structure was determined. by X-ray analysis. Formation of eight-membered caarbocyles is explained in terms of a metallacycle mechanism invovling rethenium induced C-C bond formation of the coordinated 1,3,7-octatriene ligand.
(2) A dichloro (ethelene) ruthenium (II) complex involving designed terdentate chiral auxiliary, 2,5-bis [4'- (S)-isoproploxazolin-2'-yl] pyrdine (ip-pybox) was found to be highly stereo-and enantio-selective catalyst for asymmetric cyclopropanation of terminal alkenes with seberal alkyl diazoacetates. Ethylene, carbon mono … More xide, and carbene complexes involving the RuC12(pybox) fragment were prepared, and the structures and thier chemical behavior was studied in order to elucidate reasonable mechanism. Ruthenium (II) carbenoid species derived from (C_5M_<e5>) Ru fragments were found to be efficient catalyst for metathesis polymerization of norbornene.
(3) The complex, Ru (COD) (COT), COT=1,3,5-cyclooctatriene ; COD=1,5-cyclooctadiene, induced new double cycloaddition towards two melecules of alkyl propiolates. One alkyne added to the COT ligand in a [6+2] cycloaddition mode, whereas the other to the COD ligand in a [2+2+2] one, to result in the final formation of bicyclo [4.2.2] decadiene framework.
(4) Hydrogenation of acenephtylene or aceanthrylene ligands facially coordinarted to the trinuclear rethenium carbonyl cluster followed by treatment with carbon monoxide furnished new 4,5-dihydro derivatives with a fulven partial structure.
(5) New C_<60> complexes of transition metal fragments were prepared in order to develop new ligand fields for selective C-C bond formation. Less

  • Research Products

    (22 results)

All Other

All Publications (22 results)

  • [Publications] Itoh, Kenji: "Stoichiometric and Catalytic Dimerization of Conjugated Dienes with (C_5R_5)Ru(diene)^+" Organometallics. 13. 1020-1029 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nishiyama, Hisao: "New Chiral Ruthenium Bis (Oxazolinyl) pyridine Catalyst. Efficient Asymmetric Cyclopropanation of Olefins with Diazoacetates" J. Am. Chem. Soc.116. 2223-2224 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nishiyama, Hisao: "Ruthenium (II) CCl2-Bis (oxazoliny) bipyridine Complex. Its Structure and Reactivity" Chem. Lett.1111-1114 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Park, Soon Bong: "Trimethylsilylcarbene and Bis (trimethylsilyl) Formaldehyde Azine Complexes of Chiral Bis (oxazolinyl) pyridine (dichloro) ruthenium (II)" J. Chem. Soc., Chem. Commun.1315-1316 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Masuda, Katsuyuki: "Interconversion between (C_5R_5) Ru^<IV> (allyl) and (C_5R_5) Ru^<II> (diene) Complexes" J. Organometal. Chem.473. 285-294 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagashima, Hideo: "Haptotropic Rearrangement between Two Isomers of (μ2 : η3 : η5-guaiazulene) Fe_2 (CO) _5 Revisited :" Organometallics.13. 3427-3433 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nishiyama, Hisao: "Chiral Ruthenium (II)-Bis (2-oxazolin-2-yl) pyridine Complexes. Asymmetric Catalytic Cyclopropanation of Olefins and Diazoacetates" Bull. Chem. Soc. Jap.68. 1247-1262 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagashima, Hideo: "Unusual Rate Enhancement in the RhCl(PPh_3)_3-Catalyzed Hydrosilylation by Organosilanes Having Two Si-H Groups" Organometallics. 14. 2868-2879 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nishiyama, Hisao: "Formation of a Vinylcarbene Complex of Chiral [Bis (4-isopropyloxazolin-2-yl) pyridine] dichlororuthenium (II) from 3, 3-Diphenylcyclopropene" Chem. Lett.599-600 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagashima, Hideo: "Selective Hydrogenation of Aromatic Hydrocarbons Using a Triruthenium Carbonyl Cluster as a Template to Control the Hydrogenation site :" J. Am. Chem. Soc.118. 687-688 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Nagashima, Hideo: "Organopalladium and Platinum Complexes of C60 Bearing Isonitrile Ligands" Chem. Lett.405-406 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Itoh ; Kenji, Masuda ; Katsuyuki, Fukahori ; Takahiko, Nakano ; katsuyuki, and Nagashima ; Hideo: "Stoichiometric and Catalytic Dimerization of Conjugated Dienes with (C_5R_5)Ru(diene)^+" Organometallics. 13. 1020-1029 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nishiyama ; Hisao, Itoh ; Yoshiki, Matsumoto ; Hideki, Park ; Soon Bong, and Itoh ; Kenji: "New Chiral Ruthenium Bis (oxazolinyl) pyridine Catalyst. Efficient Asymmetric Cyclopropanation of Olefins Diazoacetates" J.Am.Chem.Soc.116. 2223-2224 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nishiyama ; Hisao, Park ; Soon Bong, Haga ; Masaaki, Aoki ; katsuyuki, and Itoh ; Kenji: "Ruthenium (II) CCl_2-Bis (oxazolinyl) bipyridine Complex. Its Structure and Reactivity" Chem.Lett.1111-1114 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Park ; Soon Bong, Nishiyama ; Hisao, Haga ; Itoh ; Yoshiki, and Itoh ; Kenji: "Trimethysilylcarbene and Bis' (trimethylsilyl) Formaldehyde Azine Complexes of Chiral Bis (oxazolinyl) pyridine (dichloro) rutheniumu (II)" J.Chem.Soc., Chem.Commun.1315-1316 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Matsuda ; katsuyuki, Saitoh ; Mikio, Aoki ; katsuyuki, and Itoh ; Kenji: "Interconversion between (C_5R_5)Ru^<IV> (allyl) and (C_5R_5)Ru^<II> (diene) Complexes" J.Organometal.Chem.473. 285-294 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagashima ; Hideo, Fukahori ; Takahiko, Nobata ; Mitsuharu, Akihiro ; Nakazawa ; Mitsuhiko, and Itoh ; Kenji: "Haptotropic Rearrangement between Two Isomers of (mu2 : eta3 : eta5-guaiazulene)f_<e2> (CO)_5 Revisited : Both Therman and Photochemical Processes Induce the Haptotropic Interconversion" Organometallics. 13. 3427-3433 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nishiyama ; Hisao, Itoh ; Yoshiki, Sugawara ; Yuji, Matsumoto ; Hideki, Aoki ; Katsuyuki, and Itoh ; Kenji.: "Chiral Ruthenium (II)-Bis (2-oxazolin-2-yl) pyridine Complexes. Asymmetric Catalytic Cyclopropanation of Olefins and Diazoacetates" Bull.Chem.Soc.Jap.68. 1247-1262 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagashima ; Hideo, Tatebe ; Kazuo, Ishibashi ; Toshinori, Nakaoka ; akihito, Sakakibara ; Jun, and Itoh ; Kenji: "Unnsual Rate Enhancement in the RhCl (PPh_3) _3-Catalyzed Hydrosilylation by Orhanosilanes Having Two Si-H Groups at Appropriate Distances : Mechanistic Aspects" Organometallics. 14. 2868-2879 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nishiyama ; Hisao, Park ; soon Bong ; and Itoh ; Kenji.: "Formation of a Vinylcarbene Complex of Chiral [Bis (4-isopropyloxazolin-2-yl) pyridine] dichlororuthenium (II) from 3,3-Diphenylcyclopropene." Chem.Lett.599-600 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagashima ; Hideo, Suzuki ; Akihiro, Nobata ; MitsuharU,and Itoh ; Kenji: "Selective Hydrogenation of Aromatic Hydrocarbons Using a Triruthenium Carbonyl Cluster as a Template to Control the Hydrogenation Site : First successful Isolation of 4,5-Dihydroacenaphthylene and 4,5-Dihydroacenthrylene" J.Am.Chem.Soc.118. 687-688 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Nagashima ; Hideo, Nakazawa ; Mitsuhiko, Furukawa ; Takeshi, and Itoh ; Kenji.: "Organopalladium and Platinum Complexes of C60 Bearing Isonitrile Ligands" Chem.Lett.405-406 (1996)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 1999-03-09  

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