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Development of a New Synthetic Strategy Utilizing 6π-Azaelectrocyclization and its Synthetic Application

Research Project

Project/Area Number 13680679
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Bioorganic chemistry
Research InstitutionKwansei Gakuin University

Principal Investigator

KATSUMURA Shigeo  Kwansei Gakuin University, School of Science and Technology, Professor, 理工学部, 教授 (70047364)

Project Period (FY) 2001 – 2002
Project Status Completed (Fiscal Year 2002)
Budget Amount *help
¥3,500,000 (Direct Cost: ¥3,500,000)
Fiscal Year 2002: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 2001: ¥1,900,000 (Direct Cost: ¥1,900,000)
Keywords6π-azacyclization / phospholipase A_2 inhibitor / activation of azacyclization / molecular orbital calculation / one-pot pyridine synthesis / asymmetric 6π-azaelectrocyclization / indole alkaloid / chiral auxiliary / 酵素機能阻害機構 / フロンティア軌道相互作用 / アミノインダノール誘導体 / サレンマンガン錯体 / 不斉エポキシ化 / Ritter反応 / 光学活性エピウレイン / ジヒドロピリジン合成法 / 速やかなアザ電子環状反応 / 置換基効果 / アザトリエンの立体選択的合成 / 軌道相互作用としての理解 / インドールアルカロイドの不斉合成
Research Abstract

During the course of our recent studies on the syntheses of the enzyme inhibitors and the elucidation of their inhibitory mechanism, we have found that (E)-3-carbonyl-2, 4, 6-trienal compounds inhibit the hydrolytic ability of phospholipase A_2(PLA_2) by the formation of the dihydropyridine derivatives resulting from the reaction with the particular lysine residues of PLA_2 via the 6π-electrocyclization of the intermediary Schiff bases. The thermal cyclization of 1-azatrienes to 1, 2-dihydropyridines, which is the so-called 6π-azaelectrocyclization, is one of the well-known concerted pericyclic reactions. Although a number of examples of the 6π-azaelectrocyclization have been reported, the process required a high temperature and a long reaction time, therefore, the application of this reaction toward natural products synthesis is very limited in the literature. We succeeded in significant acceleration of the aza-electrocyclization, based on the remarkable orbital interaction between the HOMO and LUMO of the 1-aza-trienes by the combination of substituent effects. We also developed the novel one-pot substituted pyridine synthesis, and achieved the synthesis of the ocular age pigment. Furthermore, we established the novel highly stereoselective asymmetric 6π-azaelectrocyclization based on the reactions between the (E)-3-carbonyl-2, 4, 6-trienal compounds and the new chiral cis-1-amino-2-indanol derivatives using a remarkably simple operation under quite mild conditions. In addition, the developed method was applied toward the formal synthesis of an indole alkaloid, 20-epiuleine.

Report

(3 results)
  • 2002 Annual Research Report   Final Research Report Summary
  • 2001 Annual Research Report
  • Research Products

    (15 results)

All Other

All Publications (15 results)

  • [Publications] Tanaka, K., Mori, H., Yamamoto, M., Katsumura, S.: "Significant Acceleration of 6π-Azaelecirocyclization Resulting from a Remarkable Substituent Effect and Formal Synthesis of the Ocular Age Pigment A2-E by a New Method for Substituted Pyridine Synthesis"J. Org. Chem.. 66. 3099-3110 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Tanaka, K., Katsumura, S.: "Highly Stereoselective Asymmetric 6π-Azaelectrocyclization Utilizing the Novel 7-Alkyl Substituted cis-1-Amino-2-indanols : Fomal Synthesis of 20-Epiuleine"J. Am. Chem. Soc.. 124. 9660-9661 (2002)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Tanaka, K., Hata, T., Hara, H., Katsumura, S.: "Development of New Wittig Reagent, Silylfuranmethylid, and its Reactivity"Tetrahedron. (in press). (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Tanaka, K., Kobayashi, T., Miwa, J., Katsumura, S.: "Highly Stereoselective Asymmetric 6π-Azaelectrscyclization Utilizing the Novel 7-Alkyl Substituted cis-1-Amino-2-inclanols : Fomal Synthesis of 20-Epiuleine"(submitted). (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Kobayashi, T., Tanaka, K., Miwa, J., Katsumura, S.: "Synthesis of New Chiral Auxiliary for 6π-Azaelectrocyclization ; 4-and 7-Alkyl Substituted cis-1-Amino-2-indanols"(submitted). (2003)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Tanaka, K., Mori, H., Yamamoto, M., Katsumura, S.: "Significant Acceleration of 6π-Azaelectrocyclization Resulting from a Remarkable Substituent Effect and Formal Synthesis of the Ocular Age Pigment A2-E by a New Method for Substituted Pyridine Synthesis"J. Org. Chem.. 66. 3099-3110 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Tanaka, K., Katsumura, S.: "Highly Stereoselective Asymmetric 6π-Azaelectrocyclization Utilizing the Novel 7-Alkyl Substituted cis-1-Amino-2-indanols : Fomal Synthesis of 20-Epiuleine"J. Am. Chem. Soc.. 124. 9660-9661 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Tanaka, K., Hata, T., Hara, H., Katsumura, S.: "Development of New Witting Reagent, Silylfuranmethylid, and its Reactivity"Tetrahedron. (in press). (2003)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Tanaka, K., Kobayashi, T., Mori, H., Katsumura, S.: "Highly Stereoselective Asymmetric 6π-Azaelectrocyclization Utilizing the Novel 7-Alkyl Substituted cis-1-Amino-2-indanols : Fomal Synthesis of 20-Epiuleine"(submitted).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Kobayashi, T., Tanaka, K., Miwa, J., Katsumura, S.: "Synthesis of New Chiral Auxiliary for 6π-Azaelectrocyclization ; 4- and 7-Alkyl Substituted cis-1-Amino-2-indanols"(submitted).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2002 Final Research Report Summary
  • [Publications] Tanaka, K., Katsumura, S.^*: "Highly Stereoselective Asymmetric 6π-Azaelctrocyclization Utilizing the Novel 7-Alkyl Substituted cis-1-Amino-2-indanols : Formal Synthesis of 20-Epiuleine"Journal of the American Chemistry Society. 124. 9660-9661 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Furuichi, N., Katsumura, S.^* et al.: "Highly Efficient Stereocontrolled Total Synthesis of the Polyfunctional Carotenoid Peridinin"Angewandte Chemie, International Edition. 41. 1023-1026 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Hakogi, T., Katsumura, S.^* et al.: "Synthesis of Sphingomyelin Carbon Analogues as Sphingomyelinase Inhibitors"The Journal of Organic Chemistry. 67. 4839-4846 (2002)

    • Related Report
      2002 Annual Research Report
  • [Publications] Hakogi, T., Shigenari, T., Katsumura, S.^*, Igarashi, Y^* et al.: "Synthesis of Fluorescence-Labeled Sphingosine and Sphingosine 1-Phosphate ; Effective tools for Sphingosine and Sphingosine 1-Phosphate Behavior"Bioorganic & Medicinal Chemistry Letters. 13(in press). (2003)

    • Related Report
      2002 Annual Research Report
  • [Publications] Tanaka, K., Mori, H., Yamamoto, M., Katsumura, S.: "Significant Acceleration of 6π-Azaelectrocyclization Resulting from a Remarkable Substitution Effect and Synthesis of the Ocular Age Pigment A2-E"The Journal of Organic Chemistry. 66. 3099-3110 (2001)

    • Related Report
      2001 Annual Research Report

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Published: 2001-04-01   Modified: 2016-04-21  

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