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1996 Fiscal Year Final Research Report Summary

Generation of Stable Biradical Intermediates in Intramolecular Photo-Cycloaddition of Aromatic Compounds

Research Project

Project/Area Number 07640710
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionCHIBA University

Principal Investigator

YAMADA Kazutoshi  Chiba University, Department of Materials Science, Professor, 工学部, 教授 (60009230)

Co-Investigator(Kenkyū-buntansha) KISHIKAWA Keiki  Chiba University, Department of Materials Science, Assistant Professor, 工学部, 助手 (40241939)
KOHMOTO Shigeo  Chiba University, Department of Materials Science, Associate Professor, 工学部, 助教授 (90195686)
YAMAMOTO Makoto  Chiba University, Department of Materials Science, Professor, 工学部, 教授 (50039294)
Project Period (FY) 1995 – 1996
KeywordsPhoto [2+2] cycloaddition / Photo [4+2] cycloaddion / Photo [4+4] cycloaddition / Biradical intermediate / Oxygen trapping / peri-Selectivity / Solid-state photochemistry / 不斉誘起
Research Abstract

In order to establish the highly stereo and peri-selective in an aromatic photo-cycloaddition and to elucidate the involvement
of biradical intermediates, photochemical reactin of N-naphthamides and N-cimmamides were examined.,
(1) Inter- and Intra- molecular selection of photo-cycloaddition ; In the photo-cycloadditin of N-cimmanoylnaphthamides, the intramolecular cycloaddion occurred in solution and the intermolecular cycloadition was achieved in the solid state reaction depending on the substituents.
(2) The control of the peri-selectivity ; This was achieved in the photo-cycloaddition of N-1- (1-naphthyl) ethyl-cimmamides and N-1- (1-naphthyl) ethylacryl amides. In the former, the intramoleclar [4+2] cycloaddition was achieved and the [2+2] cycloaddition was achieved in the latter.
(3) Novel [2+2] photo-cycloaddition of a benzene ring with an enone double bond ; This rare example of the [2+2] photo-cycloaddition was observed in N-benzoylcimmamides.
(4) Generation of a biradical intermediate and its trapping with molecular oxygen ; The 1,8 biradical intermediate was generated in the intramolecular photo-cycloaddition of N-naphthoylnaphtamides. The generated biradical intermediate was efficiently trapped with molecular oxygen. The life time of the intermedaite was determined by laser flash photolysis.
(5) Asymmetric photo [4+4] cycloaddition ; The first example of an absolute asymmetric synthesis in aromatic photo-cycloaddion was achieved in the solid-state photochemistry of N-anthronylnaphthamieds.

  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] S.Kohmoto: "Photochemical Formal [4π+4π+2π] Cycloreversion of 7,8-Diaza-3-oxatricyclo [4.2.1.0^<2,5>] non-7-enes." J.Phys.Org.Chem.8. 799-804 (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Kohmoto: "Inter-and Intra-molecular Selectivity in the Cyclisation of N-cinnamoyl-1-naphtamides in Solid-state Photochemistry and peri Selectivity in Their Photocyclisation in Solution." J.Chem.Soc.,Perkin 1. 529-535 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Kohmoto: "On the Mechanism of the Rearrangement of 7-Vinylnorcaradienes." Tetrahedron Lett.37. 7761-7764 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Kohmoto: "Intramolecular Photocycloaddtion of Cyclopropenes.Ring Strain-Driven Hydrogen Transfer of 1,4-Biradical Intermediates." Tetrahedron Lett.37. 8879-8882 (1996)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Kishikawa: "Intramolecular Photo [4+2]cycloaddition of an Enone with a Benzene Ring." J.Chem.Soc.,Perkin 1. 77-84 (1997)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Kohmoto: "Trapping of 1,8-Biradical Intermedaites by Molecular Oxygen in Photocycloaddition of Naphthoylnaphthamides,An Evidence of Stepwise Aromatic Cyclic addition." (投稿準備中).

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] S.Kohmoto, K.Kishikawa, M.Yamamoto, and K.Yamada: "Photochemical Formal [4pi+4pi+2pi] Cycloreversion of 7,8-Diaza-3-oxatricyclo [4.2.1.0^<2,5>] non-7-enes." J.Phys.Org.Chem.8 (12). 799-804 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Kohmoto, T.Kobayashi, T.Nishio, I.Iida, K.Kishikawa, M.Yamamoto, and K.Yamada: "Inter- and Intra-molecular Selectivity in the Cyclisation of N-cinnamoyl-1-naphtamides in Solid-state Photochemistry and peri Selectivity in Their Photocyclisation in Solution." J.Chem.Soc., Perkin 1. 529-535 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Kohmoto, N.Nakayama, J.Takami, K.Kishikawa, M.Yamamoto, and K.Yamada: "On the Mechanism of the Rearrangement of 7-Vinylnorcaradienes." Tetrahedron Lett.37 (43). 7761-7764 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Kohmoto, I.Koyano, K.Kishikawa, M.Yamamoto, and K.Yamada: "Intramolecular Photocycloaddtion of Cyclopropenes. Ring Strain-Driven Hydrogen Transfer of 1,4-Biradical Intermediates." Tetrahedron Lett.37 (49). 8879-8882 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Kishikawa, S.Akimoto, S.Kohmoto, M.Yamamoto, and K.Yamada: "Intramolecular Photo [4+2] cycloaddition of an Enone with a Benzene Ring." J.Chem.Soc., Perkin 1. 77-84 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] S.Kohmoto, T.Kobayashi, J.Minami, X.Ying, K.Yamaguchi, T.Karatsu, A.Kitamura, K.Kishikawa, M.Yamamoto, and K.Yamada: "Trapping of 1,8-Biradical Intermedaites by Molecular Oxygen in Photocycloaddition of Naphthoylnaphthamides ; An Evidence of Stepwise Aromatic Cyclic addition." (Manuscript in preparation).

    • 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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