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2004 Fiscal Year Final Research Report Summary

Supramolecular Asymmetric Photochirogenesis with Biopolymers as Chiral Reaction Field

Research Project

Project/Area Number 14350487
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field 高分子合成
Research InstitutionOsaka University

Principal Investigator

WADA Takehiko  Osaka University, Graduate School of Engineering, Associate Professor, 大学院・工学研究科, 助教授 (20220957)

Project Period (FY) 2002 – 2004
KeywordsAsymmetric Photoreaction / Biopolymers / Chiral Reaction Field / Supramolecular Asymmetric Photochirogenesis / Enantio Differentiation / DNA / RNA / BSA / HSA / Chirality Control
Research Abstract

In this study, I have proposed a new strategy of asymmetric photochemistry or a new concept of "supramolecular photochirogenesis," in which the chiral information of biomolecules is transferred to or multiplied in photoproducts through the solution-phase supramolecular interaction of chiral biomolecular hosts with prochiral guest substrates and the subsequent Uni.- and bimolecular photochemical reactions of the resulting host-guest complexes. All of the examined supramolecular photochirogenic approaches, employing modified cyclodextrins, (oligo)nucleotides, DNA, RNA, and protein as chiral biomolecular hosts, were successful in creating optically active photoproducts in good optical yields. Thus, the original idea of using the supramolecular interactions of chiral biomolecules in photochemical asymmetric synthesis has been demonstrated to be useful as a novel photochirogenic methodology, and is potentially extended to the other supramolecular systems. The major findings obtained in this … More thesis may be summarized as follows.
Chapter 1 is devoted to the supramolecular enantiodifferentiating photoisomerization of (Z)-cyclooctene included and sensitized by several modified α-,β-, and/or γ-cyclodextrins possessing a variety of chromophores. The inclusion complexation behavior and the subsequent enantiodifferentiating photosensitization mechanism are discussed in detail on the basis of the substituent, solvent, and temperature effects.
In Chapter 2, the same enantiodifferentiating photoisomerization of (Z)-cyclooctene to the chiral (E)-isomer was employed as a model system to assess the sensitizing and enantiodifferentiating abilities of double stranded DNA in aqueous solution. The sensitizing and enantiodifferentiating abilities of the relevant nucleosides and single- and double-stranded oligonucleotides of different sequences are also examined to assess the origin of enantiodifferentiating photoisomerization by DNA. A novel supramolecular enantiodifferentiating photoisomerization system, employing oligonucleotides, and DNA, will be proposed.
In Chapter 3 and 4, a novel bimolecular supramolecular asymmetric photocyclodimerization of 2-anthracenecarboxylate(AC) bound to bovine and human serum albumin (BSA, HSA) and is investigated in aqueous solutions. The binding behavior of AC to BSA and HSA in aqueous solutions is first assessed and the supramolecular enantioselective photocyclodimerization is performed under a variety of conditions in order to clarify the mechanisms of binding and the subsequent photoreactions to give the optically active photocyclodimers of AC. Less

  • Research Products

    (39 results)

All 2005 2004 2003 2002 2001 Other

All Journal Article (39 results)

  • [Journal Article] Mechanism of photoisomerization of optically pure trans-2,3-diphenylcyclopropane-1-carboxylic acid derivatives2005

    • Author(s)
      J.Sivaguru, T.Wada, Y.Onigane, Y.Inoue, V.Ramamurthy
    • Journal Title

      Photochemical & Photobiological Sciences 4

      Pages: 119

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis of Peptide Ribonucleic Acid Consisting of D- and L-γ-Glutamic Acid as a Backbone Structure2005

    • Author(s)
      T.Wada, Y.Hashimoto, H.Sato, Y.Inoue
    • Journal Title

      Nucleic Acids Res. (in press)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Supramolecular Asymmetric Photoreactions2005

    • Author(s)
      T.Wada, Y.Inoue
    • Journal Title

      Organic Molecular Photochemistry (Ramamurthy, V., Inoue, Y. Ed.)(Marcel Dekker : New York)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Diastereoselective [2+2] Photocycloaddition of Stilbene to Chiral Fumarate. Direct versus Charge-Transfer Excitation2004

    • Author(s)
      H.Saito, T.Mori, T.Wada, Y.Inoue
    • Journal Title

      J Am.Chem.Soc. 126

      Pages: 1900

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Enantiodifferentiating Photoaddition of Alcohols to 1,1-Diphenylpropene in Supercritical Carbon Dioxide : Sudden Jump of Optical Yield at the Critical Density2004

    • Author(s)
      Y.Nishiyama, M.Kaneda, R.Saito, T.Mori, T.Wada, Y.Inoue
    • Journal Title

      J Am.Chem.Soc. 126

      Pages: 6568

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Pressure control of enantiodifferentiating polar addition of 1,1-diphenylpropene sensitized by chiral Naphthalenecarboxylates2004

    • Author(s)
      M.Kaneda, Y.Nishiyama, S.Asaoka, T.Mori, T.Wada, Y.Inoue
    • Journal Title

      Org.Biomol.Chem. 2

      Pages: 1295

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Enhanced Diastereoselectivity via Confinement : Diastereoselective Photoisomerization of 2,3-Diphenyl-1-benzoylcyclopropane Derivatives within Zeolites2004

    • Author(s)
      J.Sivaguru, B.Raghavan, T.Wada, Y.Origane, Y.Inoue, V.Ramamurthy
    • Journal Title

      J.Org.Chem. 69

      Pages: 5528

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Enantioselective [4+2]-cycloaddition reaction of a photochemically generated o-quinodimethane : Mechanistic details, association studies, and pressure effects2004

    • Author(s)
      B.Grosch, C.Orlebar, M.Kaneda, T.Wada, Y.Inoue, T.Bach
    • Journal Title

      Chem.-A Eur.J. 10

      Pages: 2179

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Pressure control of diastereodifferentiating [2+2] photocycloaddition of (E)-stilbene to chiral fumarate upon direct and charge-transfer excitation2004

    • Author(s)
      H.Saito, T.Mori, T.Wada, Y.Inoue
    • Journal Title

      Chem.Comm.

      Pages: 1652

    • Description
      「研究成果報告書概要(和文)」より
  • [Journal Article] Supramolecular Photochirogenesis. 3. Enantiodifferentiating Photoisomerization of Cyclooctene Included and Sensitized by 6-O-Mono(o-methoxybenzoyl)-cyclodextrin2004

    • Author(s)
      Y.Gao, M.Inoue, T.Wada, Y.Inoue
    • Journal Title

      J.Inclusion Phenomena and Macrocyclic Chem. 50

      Pages: 111

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Enantiodifferentiating Photoaddition of Alcohols to 1,1-Diphenylpropene in Supercritical Carbon Dioxide : Sudden Jump of Optical Yield at the Critical Density2004

    • Author(s)
      Y.Nishiyama, M.Kaneda, R.Saito, T.Mori, T.Wada, Y.Inoue
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 6568

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Diastereoselective [2+2] Photocycloaddition of Stilbene to Chiral Fumarate. Direct versus Charge-Transfer Excitation2004

    • Author(s)
      H.Saito, T.Mori, T.Wada, Y.Inoue
    • Journal Title

      J.Am.Chem.Soc. 126

      Pages: 1900

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] A 5'-Amino-5'-deoxyribonucleoside Containing Nucleic Acid Model for External Reversible Control of Recognition Behavior through anti-syn Orientational Switching of the Nucleobase Induced by Borate Esterification of the cis-2',3'-Diol2004

    • Author(s)
      T.Wada, H.Sato, N.Minamimoto, Y.Inoue
    • Journal Title

      Biopolym. 76

      Pages: 15

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Residue- and sequence-selective binding of nonaromatic dipeptides by bis(β-cyclodextrin) with a functional tether2004

    • Author(s)
      Y.Liu, Y.Yang, Y.Song, H.Zhang, T.Wada, Y.Inoue
    • Journal Title

      Chem.Bio.Chem. 5

      Pages: 868

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Enhanced Diastereoselectivity via Confinement : Diastereoselective Photoisomerization of 2,3-Diphenyl-1-benzoylcyclopropane Derivatives within Zeolites2004

    • Author(s)
      J.Sivaguru, B.Raghavan., T.Wada, Y.Origane, Y.Inoue, V.Ramamurthy
    • Journal Title

      J.Org.Chem. 69

      Pages: 5528

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Enhanced Diastereoselectivity via Confinement : Photoisomerization of 2,3-Diphenylcyclopropane-1-carboxylic Acid Derivatives within Zeolites2004

    • Author(s)
      J.Sivaguru, B.Raghavan., T.Wada, Y.Origane, Y.Inoue, V.Ramamurthy
    • Journal Title

      J.Org.Chem. 69

      Pages: 6533

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Active control of DNA recognition behavior of a-peptide ribonucleic acids containing basic amino acid residues by external factors2004

    • Author(s)
      H.Sato, T.Wada, Y.Inoue
    • Journal Title

      J.Bioactive and Compatible Polym. 19

      Pages: 65

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Pressure control of diastereodifferentiating [2+2]photocycloaddition of (E)-stilbene to chiral fumarate upon direct and charge-transfer excitation2004

    • Author(s)
      H.Saito, T.Mori, T.Wada, Y.Inoue
    • Journal Title

      Chem.Comm.

      Pages: 1652

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Remarkable differences in photo and thermal (acid-catalyzed) reactivities between ortho- and para-acylcyclohexadienones as essential factors determining the overall efficiency of the photo-Fries rearrangement2004

    • Author(s)
      T.Mori, M.Takamoto, H.Saito, T.Furo, T.Wada, Y.Inoue
    • Journal Title

      Chem.Lett. 33

      Pages: 256

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Isolation of cyclohexadienone intermediates in the photo-Fries rearrangement of 2,4-dimethylnaphth-1-yl and 1,4-dimethylnaphth-2-yl 2,4,6-trimethylbenzoates2004

    • Author(s)
      Mori, Tadashi, Takamoto, Makoto, Saito, Hideaki, Furo, Takahiro, Wada, Takehiko, Inoue, Yoshihisa
    • Journal Title

      Chem.Lett. 33

      Pages: 254

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Bovine Serum Albumin-Mediated Enantiodifferentiating Photocyclodimerization of 2-Anthracenecarboxylate2003

    • Author(s)
      T.Wada, M.Nishijima, T.Fujisawa, N.Sugahara, T.Mori, A.Nakamura, Y.Inoue
    • Journal Title

      J.Am.Chem.Soc. 125

      Pages: 7492

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Solid-Phase Synthesis of Peptide Ribonucleic Acids (PRNA)2003

    • Author(s)
      T.Wada, H.Sato, Y.Hashimoto, Y.Inoue
    • Journal Title

      Tetrahedron 59

      Pages: 7871

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Supra-Molecular Self-Assemblies of β-Cyclodextrins with Aromatic Tethers : Factors Governing the Helical Columnar versus Linear Channel Super-Structures2003

    • Author(s)
      Y.Liu, Z.Fan, H.Zhang, Y.Yang, F.Ding, T.Wada, Y.Inoue
    • Journal Title

      J.Org.Chem. 68

      Pages: 8345

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] A Novel Strategy for Reversible Control of Conformation and DNA/RNA Recognition of Peptide Ribonucleic Acid (PRNA) by External Factors2003

    • Author(s)
      T.Wada, H.Sato, Y.Inoue
    • Journal Title

      Nucleic Acids Research, Suppl. 3

      Pages: 213

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Pressure control of enantiodifferentiating photoisomerization of cyclooctenes sensitized by chiral benzenepolycarboxylates. The origin of discontinuous pressure dependence of the optical yield2003

    • Author(s)
      M.Kaneda, A.Nakamura, S.Asaoka, H.Ikeda, T.Wada, Y.Inoue
    • Journal Title

      Org.Biomol.Chem. 1

      Pages: 4435

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Acid-controlled photoreactions of aryl alkanoates : competition of trans-esterification, decarboxylation, Friesrearrangement and/or transposition2003

    • Author(s)
      T.Mori, M.Takamoto, T.Wada, Y.Inoue
    • Journal Title

      Photochem.Photobio.Sci. 2

      Pages: 1187

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Selective Binding of Steroids by 2,2'-Biquinoline-4,4'-dicarboxamide-Bridged Bis(β-cyclodextrin) : Fluorescence Enhancement by Guest Inclusion2003

    • Author(s)
      Y.Liu, Y.Song, H.Wang, H.Zhang, T.Wada, Y.Inoue
    • Journal Title

      J.Org.Chem. 68

      Pages: 3687

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Detail CD spectra analysis in view of angular momentum using chiral Eu(III) complexes2003

    • Author(s)
      Y.Hasegawa, T.Tomita, Y.Wada, T.Wada, Y.Inoue, S.Yanagida
    • Journal Title

      Kidorui 42

      Pages: 132

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Synthesis of Phosphoryl-Tethered β-Cyclodextrins and Their Molecular and Chiral Recognition Thermodynamics2003

    • Author(s)
      Liu, Yu, Li, Li, Li, Xiao-Yun, Zhang, Heng-Yi, Wada, Takehiko, Inoue, Yoshihisa
    • Journal Title

      J.Org.Chem. 68

      Pages: 3646

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] First synthesis, isolation and characterization of enantiomerically pure and inherently chiral resorc[4]arenes by lewis acid cyclization of a resorcinol monoalkyl ether2003

    • Author(s)
      M.Klaes, C.Agena, M.Kohler, M.Inoue, T.Wada, Y.Inoue, J.Mattay
    • Journal Title

      Eur.J.Org.Chem.

      Pages: 1404

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Microenvironmental Polarity Control of Electron-Transfer Photochirogenesis. Enantiodifferentiating Polar Addition of 1,1-Diphenyl-1-alkenes Photosensitized by Saccharide Naphthalenecarboxylates2003

    • Author(s)
      S.Asaoka, T.Wada, Y.Inoue
    • Journal Title

      J.Am.Chem.Soc. 125

      Pages: 3008

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] DNA Recognition Control of γ-PRNA and Mismatched Base Effects upon Complex Stability2002

    • Author(s)
      H.Sato, Y.Hashimoto, M.Kikkawa, T.Wada, Y.Inoue
    • Journal Title

      Nucleic Acids Res.Supple. 2

      Pages: 159

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Discontinuous pressure effect upon enantiodifferentiating photosensitized isomerization of cyclooctene2002

    • Author(s)
      M.Kaneda, S.Asaoka, H.Ikeda, T.Mori, T.Wada, Y.Inoue
    • Journal Title

      Chem.Comm.

      Pages: 1272

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] First asymmetric photosensitization in supercritical fluid. Exceptionally high pressure/density dependence of optical yield in photosensitized enantiodifferentiating isomerization of cyclooctene2002

    • Author(s)
      R.Saito, M.Kaneda, T.Wada, A.Katoh, Y.Inoue
    • Journal Title

      Chem.Lett.

      Pages: 860

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Diastereoselectivity Control in Photosensitized Addition of Methanol to (R)-(+)-Limonene2002

    • Author(s)
      S.Shim, K.Chul, S.Dong, D.Yoo, T.Wada, Y.Inoue
    • Journal Title

      J.Org.Chem. 67

      Pages: 5718

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] The first circular dichroism observation for organic radical cations : chiroptical properties of neomenthyloxy- and isobornyloxyanisole radicalcations2002

    • Author(s)
      T.Mori, J.Shinkuma, M.Sato, H.Saito, T.Wada, Y.Inoue
    • Journal Title

      Enantiomer 7

      Pages: 115

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Unique Dual Fluorescence of Sterically Congested Hexaalkyl Benzenehexacarboxylates : Mechanism and Application to Viscosity Probing2002

    • Author(s)
      Y.Inoue, P.Jiang, E.Tsukada, T.Wada, H.Shimizu, A.Tai, M.Ishikawa
    • Journal Title

      J.Am.Chem.Soc. 124

      Pages: 6942

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Highly diastereoselective photoaddition of methanol to limonene2001

    • Author(s)
      D.S.Kim, S.C.Shim, T.Wada, Y.Inoue
    • Journal Title

      Tetrahedron Lett. 42

      Pages: 4341

    • Description
      「研究成果報告書概要(欧文)」より
  • [Journal Article] Functional Artificial Nucleic Acids : Peptide Ribonucleic Acids (PRNAs)-Novel Strategy for Active Control of DNA Recognition by External Factors-

    • Author(s)
      T.Wada
    • Journal Title

      Advances in Organic Chemistry-Online (A.Rahman, Y.Hayakawa Ed)(Bentham Science Publisher Ltd., USA.)

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

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Published: 2006-07-11  

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