| Project/Area Number |
01430017
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| Research Category |
Grant-in-Aid for General Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Research Field |
Synthetic chemistry
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| Research Institution | Kyoto University |
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Principal Investigator |
ITO Yoshihiko Kyoto University, Engineering, Professor, 工学部, 教授 (40026018)
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| Co-Investigator(Kenkyū-buntansha) |
OGOSHI Hisanobu Kyoto University, Engineering, Professor, 工学部, 教授 (90026188)
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| Project Period (FY) |
1989 – 1990
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| Project Status |
Completed (Fiscal Year 1990)
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| Budget Amount *help |
¥26,000,000 (Direct Cost: ¥26,000,000)
Fiscal Year 1990: ¥3,000,000 (Direct Cost: ¥3,000,000)
Fiscal Year 1989: ¥23,000,000 (Direct Cost: ¥23,000,000)
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| Keywords | Polysilanes / Poly [sila (N-substituted)-imine] / Insertion Reaction of Isonitrile / Palladium (O) Isonitrile Complex / Insertion of Acetylenes / Skeletal Rearrangement of Polysilanes / パラジウム(O)イソニトリル錯体 / ポリ(シラエチレン) / ポリ〔シラ(Nー置換)イミン〕 / イソニトリル / アリ-ルイソニトリル |
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| 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.
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