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Design of the Molecules Bearing Specific Stereochemistry and Its Application to the Development of New Reactions

Research Project

Project/Area Number 02453141
Research Category

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

Allocation TypeSingle-year Grants
Research Field Chemical pharmacy
Research InstitutionThe University of Tokushima

Principal Investigator

NAGAO Yoshimitsu  The University of Tokushima, Faculty of Pharmaceutical Sciences, Professor, 薬学部, 教授 (40027074)

Co-Investigator(Kenkyū-buntansha) SANO Shigeki  The University of Tokushima, Faculty of Pharmaceutical Sciences, Research Associ, 薬学部, 助手 (20226038)
Project Period (FY) 1990 – 1991
Project Status Completed (Fiscal Year 1991)
Budget Amount *help
¥4,200,000 (Direct Cost: ¥4,200,000)
Fiscal Year 1991: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1990: ¥2,900,000 (Direct Cost: ¥2,900,000)
KeywordsConformational Analysis / Dynamic ^1H- and ^<13>C-NMR / X-ray Analysis / Axial Conformer / Cyclohexanone / Thiane / Bent Conformation / Sigmoid Conformation / アキシアルコンホ-マ / チアン / チアンー1ーオキシド / チアンー1,1ージオキシド / ジヒドロチイン / 軌道相互作用 / 機能性分子 / 屈折型コンホ-ション
Research Abstract

We are extensively developing a new system in which stereochemistry and reaction of the unique molecule can be regulated under the electronic control.
Conformational analysis of various six-membered ring compounds possessing alkoxy and silyloxy substituents has been performed by utilizing their dynamic <@D11@>D1H- and <@D113@>D1C-NMR, <@D1119@>D1Sn-NMR, and X-ray analyses. Thus, it was clarified that chair-type 3-silyloxy-substituted glutaric anhydride and glutarimide and the chair-type cyclohexanones possessing alkoxy or silyloxy group at the C4 position can predominantly adopt each corresponding substituent-axial conformer in their solution. Similar axial or pseudoaxial preference of silyloxy and benzyloxy groups at C4 of chair-type thiane-1-oxides, thiane-1, 1-dioxides, and dihydrothiines was recognized on their dynamic <@D11@>D1H-NMR spectra. Such axial preference of alkoxy and silyloxy groups of several six-membered compounds was also observed in their crystallographic structures. Existence of the electron-withdrawing moiety ((]SY.di-substituted left.[)C=O, (]SY.di-substituted left.[)SO, (]SY.di-substituted left.[)SO<@D22@>D2) and the low basicity of silyloxy- and alkoxy-oxygen atom proved to be essential for adopting the axial conformer, which could be rationalized in terms of a general hypothesis ; stabilization of the axial conformer due to C3, 5-Hsigma, C4-Osigma<@D1*@>D1 orbital overlap.
Several molecules, adopting a bent conformation stacked with both aromatics such as triazoles and benzene derivatives, have been developed and characterized by X-ray crystallographic and ^1H-NMR analyses. Bridging both aromatic moieties with a sulfonic ester bond seems to be an essential factor for the bent conformation. Design and synthesis of new molecules adopting a unique sigmoid conformation have been achieved on the basis of a molecular mechanic calculation.

Report

(3 results)
  • 1991 Annual Research Report   Final Research Report Summary
  • 1990 Annual Research Report
  • Research Products

    (21 results)

All Other

All Publications (21 results)

  • [Publications] Y.Nagao: "Biomimetic,Chemical,and Spectroscopic Evaluations for the Radiosensitizing Potential of N1-and N2-Substituted Derivatives of 3-Nitro-1,2,4-triazole toward Hypoxic Cells in the Radiotherapy:Remarkably Different Substitution Effect" Tetrahedron. 46. 3211-3232 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y.Nagao: "Axial Preference of Bulky Group-and Electron-Withdrawing Group-Substituted Oxygen Atom on the Chair-Type Cyclohexanone,-Glutaric Anhydride,and -Glutarimide" Chemistry Letters. 1503-1506 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y.Nagao: "Generalization,Alteration,and Enhancement of the Stereoselectivity in the Cieplak-Mode Reductions of 4-Alkoxy (or Silyoxy) cyclohexanones" Chemistry Letters. 1507-1510 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y.Nagao: "Characterization of the Sulfonic Esters Adopting a Bent Conformation Stacked with Aromatic Moieties" Chemistry Letters,.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y.Nagao: "Design and Synthesis of New Molecules Adopting a Unique Sigmoid Conformation Stacked with Aromatic Moieties" Chemistry Letters,.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y.Nagao: "Remarkably Electron-Withdrawing Effect on the Preferential Conformer of 4-Substituted Thianes,Thiane 1-Oxides,and Thiane 1,1-Dioxides" J.Am.Chem.Soc.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y.Nagao: "Preferential Conformation of the Six-Membered Ring Bearing Alkoxy (or Silyloxy) and Tributyl Stannyl Groups at the Geminal Position" J.Org.Chem.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Nagao: "Biomimetic, Chemical, and Spectorscopic Evaluations for the Radiosensitizing Potential of N1- and N2-Substituted Derivatives of 3-Nitoro-1, 2, 4-triazole toward Hypoxic Cells in the Radiotherapy : Remarkably Different Substitution Effect" Tetrahedron. 46. 3211-3232 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Nagao: "Axial Preference of Bulky Group- and Electron-Withdrawing Group-Substituted Oxygen Atom on the Chair-Type-Cyclohexanone, -Glutaric Anhydride, and -Glutarimede" Chemistry Letters. 1503-1506 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Nagao: "Generalization, Alteration, and Enhancement of the Steroselectivity in the Cieplak-Mode Reducations of 4-Alkoxy (or Silyloxy) cyclohexanones" Chemistry Letters. 1507-1510 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Nagao: "Characterization of the Sulfonic Esters Adopting a Bent Conformation Stacked with Aromatic Moieties" Chemistry Letters.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Nagao: "Design and Synthesis of New Molecules Adopting a Unique Sigmoid Conformation Stacked with Aromatic Moieties" Chemistry Letters.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Nagao: "Remarkably Electron-Withdrawing Effect on the Preferential Conformer of 4-Substituted Thianes, Thiane 1-Oxides, and Thiane 1, 1-Dioxides" J. Am. Chem. Soc.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y. Nagao: "Preferential Conformation of the Six-Membered Ring Bearing Alkoxy (or Silyloxy) and Tributyl Stannyl Groups at the Geminal Position" J. Org. Chem.

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1991 Final Research Report Summary
  • [Publications] Y.Nagao: "Remarkably ElectronーWithdrawing Effect on the Preferential Conformer of 4ーSubstituted Thianes,thiane 1ーOxides,and Thiane 1,1ーDioxides" J.Am.Chem.Soc.

    • Related Report
      1991 Annual Research Report
  • [Publications] Y.Nagao: "Preferential Conformation of the SixーMembered Ring Bearing Alkoxy (or Silyloxy) and Tributyl Stannyl Groups at the Geminal Position" J.Org.Chem.

    • Related Report
      1991 Annual Research Report
  • [Publications] Y.Nagao,S.Sano,M.Ochiai,E.Fujita: "Biomimetic,Chemical,and Spectroscopic Evaluations for the Radiosensitizing Potential of N1ーand N2ーSubstituted Derivatives of 3ーNitroー1,2,4ーtriazole toward Hypoxic Cells in the Radiotherapy:Remarkably Different Substitution Effect" Tetrahedron. 46. 3211-3232 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Y.Nagao,M.Goto,M.Ochiai,M.Shiro: "Axial Preference of Bulky Groupーand ElectronーWithdrawing GroupーSubstituted Oxygen Atom on the ChairーTypeーCyclohexanone,ーGlutaric Anhydride,and ーGlutarimide" Chemistry Letters. 1503-1506 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Y.Nagao,M.Goto,M.Ochiai: "Generalization,Alteration,and Enhancement of the Stereoselectivity in the CieplakーMode Reductions of 4ーAlkoxy(or Silyloxy)cyclohexanones" Chemistry Letters. 1507-1510 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Y.Nagao,M.Goto,Y.Kotani,K.Kida,M.Shiro: "General Explanation for Axial Preference of Silyloxy and Benzyloxy Groups at the 4ーPosition of ChairーType Thianeー1ーoxides and -1,1ーdioxides"

    • Related Report
      1990 Annual Research Report
  • [Publications] Y.Nagao,S.Sano,S.Nakagawa,M.Shiro: "Molecular Design for Novel Compounds Adopting an S_2ーSymmetric Sigmoid Conformation"

    • Related Report
      1990 Annual Research Report

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Published: 1990-04-01   Modified: 2016-04-21  

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