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1990 Fiscal Year Final Research Report Summary

Study on Synthesis and Properties of Functional Material Poly [Sila (N-Substituted) Imine]

Research Project

Project/Area Number 01430017
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionKyoto University

Principal Investigator

ITO Yoshihiko  Kyoto University, Engineering, Professor, 工学部, 教授 (40026018)

Co-Investigator(Kenkyū-buntansha) OGOSHI Hisanobu  Kyoto University, Engineering, Professor, 工学部, 教授 (90026188)
Project Period (FY) 1989 – 1990
KeywordsPolysilanes / Poly [sila (N-substituted)-imine] / Insertion Reaction of Isonitrile / Palladium (O) Isonitrile Complex / Insertion of Acetylenes / Skeletal Rearrangement of Polysilanes
Research Abstract

Palladium-catalyzed insertion reactions of isocyanides into silicon-silicon linkage of oligosilanes have been studied. A variety of disilanes reacted with aliphatic and aromatic isocyanides in the presence of palladium (O) tetrakis (triphenylphosphine) complex or palladium (II) acetate to give the corresponding bis (silyl) N-substituted imines in moderate yields. Oligosilanes were reacted with an excess of 2, 6-disubstituted aryl isocyanide in the presence of palladium (II) acetate, resulting in regular insertion of the isocyanide into each silicon-silicon linkage giving poly (silaimine) derivatives. The palladium catalyzed regular insertion was successfully achieved with up to hexasilane. Partial insertion of the isocyanide into oligosilanes was also achieved selectively by use of the limiting amount of isocyanide. New skeletal rearrangement of tetrasilanes was found in the palladium catalyzed reaction of tetrasilanes with one molar equivalent of 2, 6-disubstituted phenyl isocyanide to afford 2, 4-disila-3, 3-bis (silyl)-1-azacyclobutane derivatives, which was properly reconstituted from four fragments of tetrasilane and two fragments of isocyanide. Noteworthy is that the skeletal rearrangement was assisted by tert-alkyl isocyanide ligand on palladium catalyst.

  • Research Products

    (10 results)

All Other

All Publications (10 results)

  • [Publications] Y.ITO: "NーSubstituted Organo(silyliminomethyl)stannanes:Synthetic Equivalent to Organosilylcarbonyl Anion and Carbonyl Dianion" J.Am.Chem.Soc.109. 7888-7890 (1987)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] M.MURAKAMI: "Conjugate Addition of NーSubstituted Organo(silyliminomethyl)copper(I) to α,βーUnsaturated Carbonyl Compounds" Tetrahedron Lett.29. 355-358 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.ITO: "PalladiumーCatalyzed Regular Insertion of Isonitriles into SiliconーSilicon Linkage of Polysilane" J.Am.Chem.Soc.110. 3692-3693 (1988)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.ITO: "Novel Skeletal Rearrangement Reaction of Tetrasilanes with Aryl Isocyanides" J.Chem.Soc.,Chem.Commun.1494-1495 (1989)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.ITO: "Palladium / tertーAlkyl Isocyanide as a Highly Efficient Catalytic System for Interーand Intramolecular Bisーsilylation of Carbonーcarbon Triple Bond" J.Org.Chem.(1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y. ITO: "N-Substituted Organo (silyliminomethyl) stannanes : Synthetic Equivalent to Organosilylcarbonyl Anion and Carbonyl Dianion" J. Am. Chem. Soc.Vol. 109. 7888-7890 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] M. MURAKAMI: "Conjugate Addition of N-Substituted Organo (silyliminomethyl) copper (I) to alpha, beta-Unsaturated Carbonyl Compounds" Tetrahedron Lett.Vo1.29. 355-358 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. ITO: "Palladium-Catalyzed Regular Insertion of Isonitriles into Silicon-Silicon Linkage of Polysilane" J. Am. Chem. Soc.Vol. 110. 3692-3693 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. ITO: "Novel Skeletal Rearrangement Reaction of Tetrasilanes with Aryl Isocyanides" J. Chem. Soc., Chem. Commun.1494-1495 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. ITO: "Palladium / tert-Alkyl Isocyanide as a Highly Efficient Catalytic System for Inter- and Intramolecular Bis-silylation of Carbon-carbon Triple Bond" J. Org. Chem.(1991)

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

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Published: 1993-08-12  

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