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2004 Fiscal Year Final Research Report Summary

Study on reactive intermediates and solvent participation by means of interplay of photochemical and thermochemical reactions

Research Project

Project/Area Number 14340202
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionUniversity of Hyogo (2004)
Himeji Institute of Technology (2002-2003)

Principal Investigator

OKUYAMA Tadashi  University of Hyogo, Graduate School of Material Science, Professor, 大学院・物質理学研究科, 教授 (40029484)

Co-Investigator(Kenkyū-buntansha) FUJITA Morifumi  University of Hyogo, Graduate School of Material Science, Assistant Professor, 大学院・物質理学研究科, 助手 (00275314)
Project Period (FY) 2002 – 2004
Keywordsiodonium salt / vinyl cation / cation radical / naphthalene / cycloalkyne / neighboring group participation / singlet oxygen / laser photolysis
Research Abstract

Solvolysis of optically active 4-methylcyclohexylidenemethyl iodonium salt gives a rearranged cycloheptenyl product with complete retention of optical purity, indicating that primary vinyl cation is not formed. This was also the case even in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP), and ionic liquids as well as in a solution of high ionic strength. However, the photosolvolysis leads to racemization of the products via formation of the primary vinylic cation. The same iodonium salt leads to racemized substitution products in the presence of a base in HFIP. The racemization takes place via elimination-addition mechanism with the cycloheptyne intermediate. Thermal reaction of styryl iodonium salt occurs via beta-phenyl participation with a benzenium ion intermediate. Photoreaction of the styryl substrate also takes place via the primary vinyl cation without participation. Observation of intermediate benzenium ion via photo-generated primary vinyl cation was attempted by laser photolysis in a nanosecond time scale, but there found no indication of formation of this bridged cation.
Photo-induced cycloaddition of naphthalene derivatives carrying a chiral side chain with o-chloranil took place stereoslectively.. Laser photolysis of this solution at 355 nm showed formation of a cation radical of the naphthalene substrate. The same cation radical was thermally generated with ferric salt in HFIP solution, and circular dichroic spectra were observed showing the Cotton effects around the wavelength of absorption. This result suggests that there is some interaction between the naphthalene ring and the chiral side chain, which is considered to be responsible for the stereoselectivity of the cycloaddition. Similar naphthalene derivatives carrying a chiral carboxylate side chain were subjected to the reaction with singlet oxygen, which led to synthesis of optically active hydroperoxides.

  • Research Products

    (16 results)

All 2005 2004 2003 2002

All Journal Article (16 results)

  • [Journal Article] Michael addition-elimination mechanism for nucleophilic substitution reaction of cycloalkenyl iodonium salts and selecrivity of 1,2-hydrogen shift in cycloalkylidene intermediate2005

    • Author(s)
      藤田守文
    • Journal Title

      Journal of Organic Chemistry 70

      Pages: 480-488

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Michael addition-elimination mechanism for nucleophilic substitution reaction of cycloalkenyl iodonium salts and selecrivity of 1,2-hydrogen shift in cycloalkylidene intermediate2005

    • Author(s)
      Morifumi Fujita
    • Journal Title

      Journal of Organic Chemistry 70

      Pages: 480-488

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Elimination-addition mechanism for nucleophilic substitution reaction of cyclohexenyl iodonium salts and regioselecitity of nucleophilic addition to the cyclohexyne intermediate2004

    • Author(s)
      藤田守文
    • Journal Title

      Journal of American Chemical Society 126

      Pages: 7548-7558

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Regioselective ring opening of alkylidenecyclopropanone silyl acetals2004

    • Author(s)
      藤田守文
    • Journal Title

      Tetrahedron Letters 45

      Pages: 8023-8026

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Elimination-addition mechanism for nucleophilic substitution reaction of cyclohexenyl iodonium salts and regioselecitity of nucleophilic addition to the cyclohexyne intermediate2004

    • Author(s)
      Morifumi Fujita
    • Journal Title

      Journal of Amirican Chemical Society 126

      Pages: 7548-7558

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Regioselective ring opening of alkylidenecyclopropanone silyl acetals2004

    • Author(s)
      Morifumi Fujita
    • Journal Title

      Tetrahedron Letters 45

      Pages: 8023-8026

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Generation of cycloheptyne during the solvolysis of cyclohexylidenemethyl iodonium salts in the presence of base2003

    • Author(s)
      藤田守文
    • Journal Title

      Bulletin of Chemical Society of Japan 76

      Pages: 1849-1855

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Generation of cycloheptyne during the solvolysis of cyclohexylidenemethyl iodonium salts in the presence of base2003

    • Author(s)
      Morifumi Fujita
    • Journal Title

      Bulletin of Chemical Society of Japan 76

      Pages: 1849-1855

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Photosolvolysis of optically active 4-methylcyclohexylidenemethyl(aryl)iodonium tetrafluoroborate2002

    • Author(s)
      藤田守文
    • Journal Title

      Tetrahedron letters 43

      Pages: 8579-8581

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Cyclohexyne. Generation from iodonium salts and regioselctive reaction with nucleophile2002

    • Author(s)
      藤田守文
    • Journal Title

      Chemistry Letters 31

      Pages: 908-909

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Solvolysis of vinyl iodonium salts. New insight into vinyl cation intermediates2002

    • Author(s)
      奥山 格
    • Journal Title

      Accounts of Chemical Research 35

      Pages: 12-18

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Chirality probe approach to reactive intermediates. Primary vinyl cation and cycloalkyne2002

    • Author(s)
      奥山 格
    • Journal Title

      Proceeding of Japan Academy 78(B)

      Pages: 167-172

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Photosolvolysis of optically active 4-methylcyclohexylidene-methyl(aryl)iodonium tetrafluoroborate2002

    • Author(s)
      Morifumi Fujita
    • Journal Title

      Tetrahedron Letters 43

      Pages: 8579-8581

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Cyclohexyne. Generation from iodonium salts and regioselctive reaction with nucleophile2002

    • Author(s)
      Morifumi Fujita
    • Journal Title

      Chemistry Letters 31

      Pages: 908-909

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Solvolysis of vinyl iodonium salts. New insight into vinyl cation intermediates2002

    • Author(s)
      Tadashi Okuyama
    • Journal Title

      Accounts of Chemical Research 35

      Pages: 12-18

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Chirality probe approach to reactive intermediates. Primary vinyl cation and cycloalkyne2002

    • Author(s)
      Tadashi Okuyama
    • Journal Title

      Proceeding of Japan Academy 78(B)

      Pages: 157-172

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

URL: 

Published: 2006-07-11  

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