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Structural Studies on Reactive Complexes for Highly Selective Organic Reactions

Research Project

Project/Area Number 06557117
Research Category

Grant-in-Aid for Developmental Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field Chemical pharmacy
Research InstitutionUniversity of Tokyo

Principal Investigator

ODASHIMA Kazunori  University of Tokyo Faculty of Pharmaceutical Sciences, Associate Professor, 薬学部, 助教授 (30152507)

Co-Investigator(Kenkyū-buntansha) IMANARI Mamoru  JEOL Ltd.Application & Research Center General Manager, 分析技術本部, センター長
HIGUCHI Tsunehiko  University of Tokyo Faculty of Pharmaceutical Sciences, Assistant Professor, 薬学部, 助手 (50173159)
SODEOKA Mikiko  Sagami Chemical Research Center Senior Researcher, 副主任研究員 (60192142)
NOGUCHI Hiroshi  University of Shizuoka School of Pharmaceutical Sciences, Professor, 薬学部, 教授 (60126141)
ENDO Yasuyuki  University of Tokyo Faculty of Pharmaceutical Sciences, Associate Professor, 薬学部, 助教授 (80126002)
Project Period (FY) 1994 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥10,700,000 (Direct Cost: ¥10,700,000)
Fiscal Year 1995: ¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 1994: ¥7,000,000 (Direct Cost: ¥7,000,000)
KeywordsReactive Complex / Solution Structure / Nuclear Magnetic Resonance / Calixarene Ester / Chiral Lithium Amide / Teleocidin Analogue / Chiral Palladium Complex / Ruthenium Porphyrin / 核磁気共鳴スペクトル法 / 膜電位変化 / キラルリチウムアミド / ベンゾラクタム / ステロイドグリコシド / 不斉アルドール反応 / カリックスアレン / テレオシジン / ルシジン / 不斉Heck反応
Research Abstract

Solution structures of reactive complexes for several kinds of highly selective organic reactions have been investigated in detail by multinuclear NMR spectroscopy and other methods, and the following new results have been obtained.
1.Reactive Complexes for Membrane Potential Changes Selective changes in membrane potential, observed for dopamine and related compounds by a PVC matrix liquid membrane based on calix [6] arene hexaester, have been shown by ^1H-NMR to be based on discrimination of nonpolar moieties by cavity inclusion.
2.Reactive Complexes for Promotion of Cancer Detailed ^1H-NMR investigations on the solution structures of a series of indolactams and benzolactams, synthesized as a novel type of model compounds of TPA-type cancer promoter teleocidin, have revealed their active conformation to be the twist form.
3.Reactive Complexes for Asymmetric Reaction of Lithium Enolates Detailed ^6Li-and ^<15>N-NMR investigations have revealed that the complex leading to high selectivities in asymmetric deprotonation mediated by chiral lithium amide is its 1 : 1 mixed aggregate with LiCl.
4.Reactive Complexes for Catalytic Asymmetric C-C Bond Formation Detailed ^1H-and ^<31>P-NMR investigations have revealed the solution structures of chiral BINAP-Pd complexes leading to high selectivities of catalytic asymmetric Heck and aldol reactions.
5.Reactive Complexes for Biomimetic Catalyic Oxidation The complex leading to the high efficiencies of catalytic oxidation by Ru-porphyrin complex for unreactive alkanes and aromatic compounds has been shown to be [Ru^<VI> (por) (X) (O) ]^+ (X=Cl or Br) by ^1H-NMR and other methods.

Report

(3 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report
  • Research Products

    (41 results)

All Other

All Publications (41 results)

  • [Publications] K. Odashima: "Chemical Sensing Based on Membrane Potential Change Induced by Host-Guest Complexation at a Membrane Surface" Supramolecular Chemistry. 4. 101-113 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K. Yagi: "Channel Mimetic Sensing Membranes for Alkali Metal Cations Based on Oriented Monolayers of Calixarene Esters" Journal of Electroanalytical Chemistry. 401. 65-79 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y. Endo: "Chiral Requirements for Tumor Promoters : Conformations and Activity of Benzolactams" Bioorg. Med. Chem. Lett.4. 491-494 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y. Endo: "Synthesis, Conformation, and Biological Activity of Teleocidin Mimics, Benzolactams. Structure-Activity Studies of Teleocidins." J. Am. Chem. Soc.118(in press). (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y. Kawasaki: "Identification of Adducts Formed by Reaction of Purine Bases with a Mutagenic Anthra-quinone, Lucidin : Mechanism of Mutagenicity" Dhem. Pharm. Bull.42. 1971-1973 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K. Inoue: "Spirostanol and Furostanol Glycosides of Costus speciosus (KOENIG.)SM." Natural Medicines. 49. 336-339 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K. Ohrai: "Effects of Solvents and Additives in the Asymmetric Heck Reaction of Alkenyl Triflates : Catalytic Asymmetric Synthesis of Decalins" J. Am. Chem. Soc.116. 11737-11748 (1994)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M. Sodeoka: "Catalytic Asymmetric Aldol Reaction Via Chiral Pd(II) Enolate in Wet DMF" J. Org. Chem.60. 2648-2649 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M. Komuro: "Application of Chemical Cytochrome P-450 Model Systems to studies on Drug Metabolism-VIII. Novel Metabolism, of Carboxylic Acids" Bioorg. Med. Chem.3. 55-65 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] H. Ohtake: "The Highly Efficient Oxidation of Olefins, Alcohols, Sulfides and Alkanes with Heteroaromatic N-Oxides Catalyzed by Porphyrins" Heterocyles. 40. 867-903 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K. Koga: "Approaches to Catalytic Asymmertric Formation and Reactions of Lithium Enolates" J. Synth. Org. Chem., Jpn.53. 1021-1032 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 小田嶋和徳: "膜電位変化を伴うホストーゲスト分子認識" 薬学雑誌. 115. 431-445 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K. Odashima: "Molecular Recognition : Receptors for Molecular Guests (Comprehensive Supramolecular Chemistry)" Pergamon Press (in press), (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] 小田嶋和徳: "超分子化学への道" 学会出版センター, (印刷中) (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Odashima, R.Naganawa, H.Radecka, M.Kataoka, E.Kimura, T.Koike, K.Tohda, M.Tange, H.Furuta, J.L.Sessler, K.Yagi, and Y.Umezawa: ""Chemical Sensing Based on Membrane Potential Change Induced by Host-Guest Complexation at a Membrane Surface"" Supramol.Chem.4. 101-113 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Yagi, S.B.Khoo, M.Sugawara, T.Sakaki, S.Shinkai, K.Odashima, and Y.Umezawa: ""Channel Mimetic Sensing Membranes for Alkali Metal Cations Based on Oriented Monolayrs of Calixarene Esters"" J.Electroanal.Chem.401. 65-79 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Endo, M.Ohno, M.Hirano, M.Takeda, A.Itai, and K.Shudo: ""Chiral Requirements for Tumor Promoters : Conformations and Activity of Benzolactams"" Bioorg.Med.Chem.Lett.4. 491-494 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Endo, M.Ohno, M,Hirano, A.Itai, and K.Shudo: ""Synthesis, Conformation, and Biological Activity of Teleocidin Mimics, Benzolactams. A Clarification of the Conformational Flexibility Problem in Structure-Activity Studies of Teleocidins"" J.Am.Chem.Soc.118 (in press). (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Kawasaki, Y.Goda, H.Noguchi, and T.Yamada: ""Identification of Adducts Formed by Reaction of Purine Bases with a Mutagenic Anthraquinone, Lucidin : Mechanism of Mutagenicity by Anthraquinones Occurring in Rubiaceae Plants"" Chem.Pharm.Bull.42. 1971-1973 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Inoue, S.Kobayashi, H.Noguchi, U.Sankawa, and Y.Ebizuka: ""Spirostanol and Furostanol Glycosides of Costus speciosus (KOENIG.) SM."" Natural Medicines. 49. 336-339 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Ohrai, K.Kondo, M.Sodeoka, and M.Shibasaki: ""Effects of Solvents and Additives in the Asymmetric Heck Reaction of Alkenyl Triflates : Catalytic Asymmetric Synthesis of Decalin Derivatives and Determination of the Absolute Stereochemistry of (+)-Vernolepin"" J.Am.Chem.Soc.116. 11737-11748 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Sodeoka, K.Ohrai, and M.Shibasaki: ""Catalytic Asymmetric Aldol Reaction via Chiral Pd (II) Enolate in Wet DMF"" J.Org.Chem.60. 2648-2649 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] M.Komuro, T.Higuchi, and M.Hirobe: ""Application of Chemical Cytochrome P-450 Model Systems to Studies on Drug Metabolism - VIII.Novel Metabolism of Carboxylic Acids via Oxidative Decarboxylation"" Bioorg.Med.Chem.3. 55-65 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] H.Ohtake, T.Higuchi, and M.Hirobe: ""The Highly Efficient Oxidation of Olefins, Alcohols, Sulfides and Alkanes with Heteroaromatic N-Oxides Catalyzed by Ruthenium Porphyrins"" Heterocycles. 40. 867-903 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K.Koga and M.Shindo: ""Approaches to Catalytic Asymmetric Formation and Reactions of Lithium Enolates"" J.Synth.Org.Chem., Jpn.53. 1021-1032 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] K. Yagi: "Channel Mimetic Sensing Membranes for Alkali Metal Cations Based on Calixarene Esters" Journal of Electroanalytical Chemistry. in press (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] T. Takahashi: "Enantioselective Darzens Reaction: Asymmetric Synthesis of trans-Glycidic Esters" Chemical and Pharmaceutical Bulletin. 43. 1821-1823 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] Y. Endo: "Synthesis, Conformation, and Biological Activity of Teleocidin Mimics, Benzolactams" Journal of the American Chemical Society. 118. in press (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] K. Inoue: "Spirostanol and Furostanol Glycosides of Costus speciosus (KOENIG.) SM." Natural Medicines. 49. 336-339 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] M. Sodeoka: "Catalytic Asymmetric Aldol Reaction via Chiral pd(II) Enolate in Wet DMF" Journal of Organic Chemistry. 60. 2648-2649 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] T. Higuchi: "Selective Quinone Formation by Aromatic Oxidation with Heteroaromatic N-Oxide by Ruthenium Porphyrin" Journal of the American Chemical Society. 117. 8879-8880 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] K.Odashima: "Comprehensive Supramolecular Chemistry Molecular Recognition: Receptors for Molecular Gusets" Elsevier Science(in press), (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] 小田嶋和徳: "超分子化学への道" 学会出版センター(印刷中), (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] K.Odashima: "Chemical Sensing Based on Membrane Potential Change Induced by Host-Guest Complexation" Supramolecular Chemistry. 4. 101-114 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] K.Manabe: "2+2 Salt Formation Induced by Hydrogen Bonding" Tetrahedron Letters. 35. 2705-2708 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Y.Endo: "Chiral Requirements for Tumor Promoters:Conformations and Activity of Benzolactams" Bioorg.Med.Chem.Lett.4. 491-494 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Y.Kawasaki: "Identification of Adducts Formed by Reaction of Purine Bases with a Mutagenic Anthraquinone,Lucidin" Chemical and Pharmaceutical Bulletin. 42. 1971-1973 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] K.Ohrai: "Effects of Solvents and Additives in the Asymmetric Heck Reaction of Alkenyl Triflates" Journal of the American Chemical Society. 116. 11737-11748 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] H.Ohtake: "The Highly Efficient Oxidation of Olefins,Alcohols,Sulfides and Alkanes by Ruthenium Porphyrins" Heterocycles. 38. in press (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] K.Odashima: "Molecular Recognition:Receptors for Molecular Guests" Pergamon Press, in press (1995)

    • Related Report
      1994 Annual Research Report
  • [Publications] K.Koga: "Pure & Applied Chemistry" Asymmetric Synthesis Mediated by Chiral Ligands, 6 (1994)

    • Related Report
      1994 Annual Research Report

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Published: 1994-04-01   Modified: 2016-04-21  

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