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1992 Fiscal Year Final Research Report Summary

Selective C-H Bond Activation by Group 7 and 8 Transition Metal Complexes and its Application to Organic Synthesis

Research Project

Project/Area Number 03453099
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionTokyo University of Agriculture and Technology

Principal Investigator

KOMIYA Sanshiro  Tokyo University of Agriculture and Technology, Faculty of Technology Professor, 工学部, 教授 (00111667)

Co-Investigator(Kenkyū-buntansha) FUKUOKA Atsushi  Tokyo University of Agriculture and Technology, Faculty of Technology Assistant, 工学部, 講師 (80189927)
Project Period (FY) 1991 – 1992
KeywordsRuthenium / Rhenium / Oxidative Addition / Cyanoacetate / Aldol Reaction / Michael Reaction / Enolate
Research Abstract

The objects of this research are development of novel C-H bond activation of functionalized organic substances using group 7 and 8 transition metal complexes and its application to selective organic syntheses. In this research, new rhenium, iron, and ruthenium complexes, which can smoothly produce reactive coordinatively unsaturated species, are successfully prepared. They are ReH(C_2H_4)_2(PMe_2Ph)_3 (1), ReH(N_2)(PMe_2Ph)_4 (2), [MnMe_2(dmpe)_2]^+[AlMe_4]^- (3), [MnMe_2(dmpe)_2]^+[BPh_4]^- (4), RuH_2(PPh_3)_4 (5), Ru(C_2H_4)(PPh_3)_3 (6), Fe(N_2)(depe)_2 (7), Complexes 2,5, and 6 react with active hydrogen compounds to give hydride complexes having an enolate anionic ligand. Enolate complexes derived from alpha-cyanocarboxylates have direct coordination of the cyano group to the metal leaving a highly nucleophlic enolate moiety. These complexes smoothly react with aldehydes and acrylonitrile to give aldol reaction and Michael addition products respectively. In contrast, enolate compl … More exes, which are produced by the reaction of 5 and 6 with 2,4- pentanedione, do not react with these compounds. All these complexes 2,5,6 and the enolate complexes thus prepared as well as Ru(cod)(cot)/PR_3 system act as selective catalysts of these reactions. These results indicate that the enolate complexes isolated in this research are active reaction intermediates, and support the unusually high selectivity of the ruthenium and rhenium catalyzed aldol and Michael type reactions.
On the other hand, the C-H bonds of alkenecarboxylates oxidatively add selectively to ruthenium(0) to give new hydridoalkenyl and hydrido-pi-allyl type complexes, depending on the esters employed. In the latter case, dienecarboxylate type complexes are gradually formed by the beta-hydrogen elimination from a sigma-allyl intermediate. The regeiselectivity in these CH bond activation reactions can be understood by the thermodydamic stability of the ruthenim products.
Unusual olefin metathesis reaction between coordinated alpha-cyanocinnamate on rhenium and tetracyanoethylene takes place under ambient conditions. The reaction is considered as the first example of olefin metathesis of functionalized olefins. Less

  • Research Products

    (26 results)

All Other

All Publications (26 results)

  • [Publications] Sanshiro Komiya: "Synthesis,Structure,and Reactions of Cationic Dimethylmanganese(III)Complexes Containing 1,2-Bis(dimethylphosphino)ethane Ligands" Organometallics. 10. 1311-1316 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Sanshiro Komiya: "Synthesis and Structure of Hydrido Bis(ethylene)and Hydrido Dinitrogen Complexes of Rhenium(I)Havinf Dimethylphenylphosphine Ligands" Organometallics. 10. 3105-3110 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Takuo Sone: "Dimethylgold(III)arylosides and Alkoxides Having a Tripgenylphosphine Ligand" Chem.Lett.1949-1952 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yuji Mizuho: "C-H Bond Activation by Ruthenium(0)Complexes.Isolation of an Active Intermediate in the Ruthenium Catalyzed Aldol and Michael Reactions" Chem.Lett.2127-2130 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Atsushi Fukuoka: "New Ruthenium-Molybudenum and-tungsten Heterodinuclear Complexes with trans-Styryl Ligand" Chem.Lett.69-72 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Sanshiro Komiya: "Synthesis,Structure,and Properties of Dimethyl(alkoxycarbonyl)gold(III)Having a Triphenylphosphine Ligand" J.Organomet.Chem.428. 303-313 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Sanshiro Komiya: "Selective Formation and Reactions of Tetraalkylaurates(III)" J.Organomet.Chem. 433. 337-351 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Sanshiro Komiya: "Isolation of Tetraalkylaurates(III)Having a Tetraalkylammonium Cation." Inorg.Chem.31. 3168-3169 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Sanshiro Komiya: "Isolation of Highly Nuclepohilic Gold(I)Alkoxides Having a Tertiary Phosphine Ligand." J.Chem.Soc.,Chem.Commun.1109-1110 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Sanshiro Komiya: "Associative Exchange of a Guanosine Ligand on Triphenylphos-phinegold(I)Complexes" Chem.Lett.457-460 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Sanshiro Komiya: "Isolation of a Zerovalent Iron Dinitrogen Complex with 1,2-Bis-(diethylphoshpino)ethane Ligand." J.Chem.Soc.,Chem.Commun.

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 山本 明夫: "有機金属化合物ー合成法と利用法(分担)" 東京化学同人, 320 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 伊藤 卓: "季刊化学総説No.17「前周期遷移金属の有機化学」(分担)" 学会出版センター, 220 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Sanshiro Komiya, Tomoya Kimura, Mitsuhiro Kaneda: "Synthesis, Structure, and Reactions of Cationic Dimethyl-manganese(III) Complexes Containing 1,2-Bis(dimethylphos-phino)ethane Ligands" Organometallics. 10. 1311-1316 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Sanshiro Komiya, Atsushi Baba: "Synthesis and Structure of Hydrido Bis(ethylene) and Hydrido Dinitrogen Complexes of Rhenium(I) Having Dimethylphenyl-phosphine Ligands." Organometallics. 10. 3105-3110 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Yuji Mizuho, Noriko Kasuga, and Sanshiro Komiya: "C-H Bond Activation by Ruthenium(0) Complexes. Isolation of an Active Intermediate in the Ruthenium Catalyzed Aldol and Michael Reactions." Chem. Lett.(12). 2127-2130 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Takuo Sone, Minori Iwata, Noriko Kasuga, and Sanshiro Komiya: "Dimethylgold(III) Aryloxides and Alkoxides Having a Triphenyl-phosphine Ligand." Chem. Lett.(11). 1949-1952 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Atsushi Fukuoka, Nobutoshi Ohashi, and Sanshiro Komiya: "New Ruthenium-Molybdenum and-Tungsten Heterodinuclear Complexes with trans Styryl Ligand." Chem. Lett.(1). 69-72 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Sanshiro Komiya, Takuo, Sone, Satoshi Ozaki, Makoto Ishikawa, Noriko Kasuga: "Synthesis, Structure and Properties of Dimethyl(alkoxycarbonyl)- gold(III) Complexes Having a Triphenylphosphine Ligand" J. Organomet. Chem.428. 303-313 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Sanshiro Komiya, Satoshi Ozaki, Isao Endo, Kunihiko Inoue, Noriko Kasuga, and Yasushi Ishizaki: "Selective Formation and Reactions of Tetraalkylaurates(III)" J. Organomet. Chem.433. 337-351 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Sanshiro Komiya, Shinichiro Ochiai, and Yasushi Ishizaki: "Isolation of Tetraalkylaurates(III) Having a Tetraalkylammonium Cation." Inorg. Chem.31. 3168-3169 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Sanshiro Komiya, Minori Iwata, Takuo Sone, and Atsushi Fukuoka: "Isolation of Highly Nucleophilic Gold(I) Alkoxides Having a Tertiary Phosphine Ligand." J. Chem. Soc., Chem. Commun.1109-1110 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Sanshiro Komiya, Koji Nakada, Mitsuru Nakada, and Atsushi Fukuoka: "Associative Exchange of a Guanosine Ligand on Triphenylphos-phinegold(I) Complexes" Chem. Lett.457-460 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Sanshiro Komiya, Masatoshi Akita, Akira Yoza, Noriko Kasuga, Atsushi Fukuoka, and Yasushi Kai: "Isolation of a Zerovalent Iron Dinitrogen Complex with 1,2-Bis- (diethylphoshpino)ethane Ligand." J. Chem. Soc., Chem. Commun.

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Akio Yamamoto: Tokyo Kagaku Dojin. Organometallic compounds-Synthesis and Utilization (allotment), 320 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Takashi Ito: Gakkai Shuppan Center. Organic Chemistry of Early Transition Metals (allotment), 220 (1993)

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

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Published: 1994-03-24  

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