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2001 Fiscal Year Final Research Report Summary

Transition-Metal Reactions of small-ring silicon compounds

Research Project

Project/Area Number 12650858
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionKawasaki University of Sciense and the Arts

Principal Investigator

ISHIKAWA Mitsuo  College of Sciense and Industrial Technology,department of Chemical Technology. professor, 産業科学技術学部, 教授 (20025985)

Co-Investigator(Kenkyū-buntansha) NAKA Akinobu  College of Science and Industrial Technology, Department of Chemical Technology, Lecture, 産業科学技術学部, 講師 (00289232)
Project Period (FY) 2000 – 2001
KeywordsSilicon / Transition-metal / Catalyzed Reaction / Cyclobutenc / Cyclopentane / Stereochemistry
Research Abstract

In this paper we report the transition-metal reactions of small-ring compounds containing silicon-silicon bond. The palladium-catalyzed reactions of pure cis-and trans-3, 4-benzo-1, 2-di(tert-butyl)-1, 2-dimethyl1, 2-disilacyclobut-3-ene (1a and 1b) with phenylacetylene and 1-hexyne produced stereospecifically cis-and trans-5, 6-benzo-1, 4-disilacyclohexa-2, 5-dienes.
The Wurtz type coupling of a mixture of meso-and dl-1, 3-bis (chloromethylphenylsilyl) propanes with sodium metal afforded a mixture of cis-and trans-disilacyclopentanes (2a and 2b) in a ratio of 1 : 1.The palladium-catalyzed reactions of 2a and 2b with phenylacetylene gave stereospecifically cis-and trans-1, 4-dimethyl-1, 2, 4-triphenyl-1, 4-disilacyclohept-2-enes (3a and 3b), in high yields. Similar treatment of 2a and 2b with diphenylacetylene also proceeded with high stereospecificity to give cis-and trans-1, 4-dimethyl-1, 2, 3, 4-tetraphenyl-1, 4-disilacyclohept-2-enes (4a and 4b), respectively.
The platinum-catalyzed … More reactions of 2a with terminal acetylenes such as phenylacetylene and 1-hexyne in a degassed sealed tube at 150℃ for 24h afforded cis-1, 4-dimethyl-1, 2, 4-triphenyl-1, 4-disilacyclohept-2-ene (5a) and cis-2-n-butyl-1, 4-dimethyl-1, 4-diphenyl-1, 4-disilacyclohept-2-ene (6a), respectively, arising from insertion of a triple bond in the acetylenes into a silicon-silicon bond. Similar reactions of 2b with phenylacetylene and 1-hexyne gave trans-1, 4-dimethyl-1, 2, 4-triphenyl-1, 4-disilacyclohept-2-ene (5b) and trans-2-n-butyl-1, 4-dimethyl-1, 4-diphenyl-1, 4-disilacyclohept-2-ene (6b), respectively. The platinum-catalyzed reactions of 2a and 2b with di-substituted acetylenes such as diphenylacetylene, 1-phenyl-1-propyne, and 3-hexyne gave the respective cis-and trans-1, 4-dimetnyl-1, 4-diphenyl-1, 4-disilacyclohept-2-ene derivatives with high stereospecificity. The nickel-catalyzed reactions of 2a and 2b with di-substituted acetylenes also proceeded with high stereospecificity to give the adducts as observed in the platinum-catalyzed reactions.
The palladium-catalyzed reaction of 1, 1-dimethyl-2, 2-diphenyl-1, 2-disilacyclopentane (7) with phenylacetylene gave regiospecifically 4, 4-dimethyl-1, 1, 2-triphenyl-1, 4-disilacyclohept-2-ene (8) in 93% yield. Similar treatment of 7 with tert-butylacetylene and 1-hexyne also proceeded with high regiospecificity to give 2-tert-butyl-4, 4-dimethyl-1, 1-diphenyl-1, 4-disilacyclohept-2-ene (9) and 2-n-butyl-4, 4-dimethyl-1, 1-diphenyl-1, 4-disilacyclohept-2-ene (10) in 93% and 90% yields, respectively. The platinum-catalyzed reactions of 7 with phenylacetylene, tert-butylacetylene, and 1-hexyne afforded regiospecifically the same products as those obtained from palladium-catalyzed reactions in high yields. Less

  • Research Products

    (10 results)

All Other

All Publications (10 results)

  • [Publications] Mitsuo Ishikawa: "Synthesis and Stereochemistry of cis-and trans-3,4-Benzo-1,2-di(tert-butyl)-1,2-dimethyl-1,2-disilacyclobutene"Organometallics. 20. 1059-1061 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Akinobu Naka: "Stereochemistry of Disilanylene-Containing Cyclic Compounds.Synthesis and Reactions of cis-and trans-1,2-Dimethyl-1,2-diphenyl-1,2-disilacyclopentanes"Organometallics. 20. 1204-1209 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Akinobu Naka: "Regiochemistry of Disilanylene-Containing Cyclic Compounds.Palladium-and Platinum-Catalyzed Reactions of 1,1-Dimethyl-2,2-diphenyl-1,2-disilacyclopentane"Organometallics. 20. 1695-1698 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Seung-Cha: "Stereochemistry of Disilanylene-Containing Cyclic Compounds.Synthesis and Reactions of cis-and trans-1,2-Dimethyl-1,2-diphenyl-1,2-disilacyclohexane"Organometallics. 20. 3718-3723 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Akinobu Naka: "Platinum-and nickel-catalyzed reactons of 1,2-dimethyl-1,2-diphenyl-1,2-disilacyclopentane with alkynes"Journal of Organometallic Chemistry. (in press).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Mitsuo, Ishikawa. Junnai, Ikadai. Akinobu, Naka. Joji, Ohshita.Atsutaka, Kunai.Kazunari, Yoshizawa. Song-Yun Kang. And Tokio, Yamabe: "Synthesis and Stereochemistry of cis-and trans-3, 4-Benzo-1, 2-di(tert-butyl)-1, 2-dimethy1-1, 2-disilacyclo-butene"Organometallics. 20(6). 1059-1061 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Akinobu, Naka.Kouhei, Yoshida.Mitsuo, Ishikawa.Ikuko, Miyahara.Ken, Hirotsu.Seung-Hun, Cha.Kyung, Koo, Lee. And Young-Woo, Kwak: "Stereochemistry of Disilanylene-containing Cyclic Compounds. Synthesis and Reactions of cis- and trans-1, 2-Dimethy1-1, 2-disilacyclopentanes"Oragnometallics. 20(6). 1204-1209 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Akinobu, Naka. And Mitsuo, Ishikawa: "Regiochemistry of Disilanylene-Containing Cyclic Compounds. Palladium- and Platinum-Catalyzed Reactions of 1, 1-Dimethy1-2, 2-dipheny1-1, 2-disilacyclo-pentane"Organometallics. 20(8). 1695-1698 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Seung-Hun, Cha. Kyung, Koo, Lee. Young-Woo, Kwak. Heung-Jin, Choi. Yeon, Sil, Park. Akinobu, Naka. And Mitsuo, Ishikawa: "Stereochemistry of Disilanylene-Containing Cyclic Compounds. Synthesis and Reactions of cis- and trans-1, 2-Dimethy1-1, 2-dipheny1-1, 2-disilacyclohexanee"Organometallics. 20(17). 3718-3723 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Akinobu, Naka. Mitsuo, Ishikawa. Seung-Hun, Cha. Kyung, Koo, Lee. And Young-Woo, Kwak: "Platinum-and nickel-catalyzed reactons of 1, 2-dimethy1-1, 2-dipheny1-1, 2-disilacyclopentane with alkynes"Journal of Organometallic Chemistry. (in press).

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

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Published: 2003-09-17  

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