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1992 Fiscal Year Final Research Report Summary

Molecular Design of New Optically Active Sensitizers for Highly Efficient Photosensitized Asymmetric Reactions

Research Project

Project/Area Number 03805080
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionHimeji Institute of Technology

Principal Investigator

INOUE Yoshihisa  Himeji Inst. of Tech., Faculty of Science, Assoc. Prof., 理学部, 助教授 (30112543)

Co-Investigator(Kenkyū-buntansha) TAI Akira  Himeji Inst. of Tech., Faculty of Science, Professor, 理学部, 教授 (20029961)
Project Period (FY) 1991 – 1992
KeywordsPhotochemistry / Asymmetric reaction / Photoisomerization / Aromatic ester
Research Abstract

In the present study, we first examined the enantiodifferentiating photoisomerizations of prochiral cycloalkenes and cyclopropanes sensitized by several aromatic esters of naturally occurring optically active alcohols to give the optical yields (o.y.) of up to 40%. In order to enhance the product s o.y., we designed a variety of novel chiral sensitizers carrying bulky and/or electron-donating substituents with the aid of molecular mechanics and molecular orbital calculations. These tailored photosensitizers afforded exceptionally high, as enantiodifferentiating photosensitizations, o. y. s. of >50% at room temperature (r. t.) and of up to 70% at -90゚C
The above encouraging results prompted us to investigate the more difficult, never tried area of photochemistry : enantiodifferentiating photoaddition reactions. Thus, the enantiodifferentiating anti-Markovnikov methanol addition to 1,1-diphenylpropene sensitized by chiral naphthalene(di) carboxylates gave the o. y. s up to 27% even at r. t.
The present work clearly indicates that the photosensitized enantiodifferentiating uni- and bimolecular reactions, demanding only a catalytic amount of chiral sensitizer, are not only of theoretical interest but also of practical importance in the asymmetric synthesis.

  • Research Products

    (21 results)

All Other

All Publications (21 results)

  • [Publications] N.Yamasaki,Y.Inoue,T.Yokoyama,A.Tai,A.Ishida and S.Takamuku: "Steric Hindrance-Induced Dual Fluorescence of Congested Benzenehexacarboxylates" J.Am.Chem.Soc.113. 1933-1941 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Inoue,M.Ouchi,K.Hosoyama,T.Hakushi,Y.Liu and Y.Takeda: "Molecular Design of Crown Ethers.8.Substitution and Lariat Effect upon Cation Complex-ation with 16-Crown-5 Derivatives in Solvent Extraction and in Homogeneous Solution" J.Chem.Soc.,Dalton Trans.1291-1293 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Inoue,H.Shimoyama,N.Yamasaki and A.Tai: "Enantiodifferentiating Photoisomerization of 1,2-Diphenylcyclopropane Sensitized by Chiral Aromatic Esters" Chem.Lett.593-596 (1991)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Inoue: "Asymmetric Photochemical Reactions in Solution" Chem.Rev.92. 741-770 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Inoue,N.Yamasaki,T.Yokoyama and A.Tai: "Enantio-differentiating Z-E Photoisomerization of Cyclooctene Sensitized by Chiral Polyalkyl Benzenepolycarboxylates" J.Org.Chem.57. 1332-1345 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Inoue,T.Okano,N.Yamasaki and A.Tai: "Enantiodifferentiating Photocyclodimerization of Phenyl Vinyl Ethers and 4-Methoxy-styrene Sensitized by Chiral Aromatic Esters" J.Photochem.Photobiol.A:Chem.66. 61-68 (1992)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Inoue,N.Yamasaki,H.Shimoyama,and A.Tai: "Enantio-differentiating cis-trans Photoisomerization of 1,2-Diarylcyclo-propanes and 2,3-Diphenyloxirane Sensitized by Chiral Aromatic Esters" J.Org.Chem.58. (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Inoue,S.Kosaka,K.Matsumoto,H.Tsuneishi,T.Hakushi,A.Tai,K.Nakagawa,and L.-H.Tong: "Vacuum UV Photochemistry in Cyclodextrin Cavity.Solid-State Z-E Photoisomerization of Cyclooctene-β-Cyclodextrin Inclusion Complex" J.Photochem.Photobiol.,A:Chem.(1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Inoue,N.Yamasaki,T.Yokoyama,and A.Tai: "Highly Enantio-differentiating Photoisomerization of Cyclooctene by Congested and/or Triplex-Forming Chiral Sensitizers" J.Org.Chem.58. (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Tsuneishi,Y.Inoue,T.Hakushi,and A.Tai: "Direct and Sensitized Geometrical Photoisomerization of 1-Methylcyclooctene" J.Chem.Soc.,Perkin Trans.2. (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Inoue,T.Okano,N.Yamasaki,and A.Tai: "First Photosensitized Enantiodifferentiating Polar Addition:Anti-Markovnikov Methanol Addition to 1,1-Diphenylpropene" J.Chem.Soc.,Chem.Commun.(1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] N. Yamasaki, Y. Inoue, T. Yokoyama, A. Tai, A. Ishida and S. Takamuku: "Steric Hindrance-Induced Dual Fluorescence of Congested Benzenehexacarboxylates" J. Am. Chem. Soc.113. 1933-1941 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Inoue, H. Shimoyama, N. Yamasaki and A. Tai: "Enantiodifferentiating Photoisomerization of 1,2-Diphenylcyclopropane Sensitized by Chiral Aromatic Esters" Chem. Lett. 593-596 (1991)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Inoue: "Asymmetric Photochemical Reactions in Solution" Chem. Rev.92. 741-770 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Inoue, N. Yamasaki, T. Yokoyama and A. Tai: "Enantio-differentiating Z-E Photo-isomerization of Cyclooctene Sensitized by Chiral Polyalkyl Benzenepolycarboxylates, J. Org. Chem." 57. 1332-1345 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Inoue, T. Okano, N. Yamasaki and A. Tai: "Enantiodifferentiating Photocyclodimerization of Phenyl Vinyl Ethers and 4-Methoxystyrene Sensitized by Chiral Aromatic Esters, J. Photochem. Photobiol. A" Chem.66. 61-68 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Inoue, N. Yamasaki, H. Shimoyama, and A. Tai: "Enantiodifferentiating cis-trans Photoisomerization of 1,2-Diarylcyclopropanes and 2,3-Diphenyloxirane Sensitized by Chiral Aromatic Esters" J. Org. Chem.58. (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Inoue, S. Kosaka, K. Matsumoto, H. Tsuneishi, T. Hakushi, A. Tai, K. Nakagawa, and L.-H. Tong: "Vacuum UV Photochemistry in Cyclodextrin Cavity. Solid-State Z-E Photo-isomerization of Cyclooctene-beta-Cyclodextrin Inclusion Complex" J. Photochem. Photobiol., A : Chem.(1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Inoue, N. Yamasaki, T. Yokoyama, and A. Tai: "Highly Enantiodifferentiating Photo-isomerization of Cyclooctene by Congested and/or Triplex-Forming Chiral Sensitizers" J. Org. Chem.58. (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H. Tsuneishi, Y. Inoue, T. Hakushi, and A. Tai: "Direct and Sensitized Geometrical Photoisomerization of 1-Methylcyclooctene" J. Chem. Soc., Perkin Trans. 2. (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y. Inoue, T. Okano, N. Yamasaki, and A. Tai: "First Photosensitized Enantiodifferentiating Polar Addition Anti-Markovnikov Methanol Addition to 1,1-Diphenylpropene" J. Chem. Soc., Chem. Commun.(1993)

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

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Published: 1994-03-24  

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