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7-Endo Selective Friedel-Crafts Cycylization of Vinylepoxides

Research Project

Project/Area Number 15590017
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionKogakuin University (2004-2006)
Hokkaido Pharmaceutical University School of Pharmacy (2003)

Principal Investigator

NAGUMO Shinji  Kogakuin University, Applied Chemistry, Associate Professor (40246765)

Project Period (FY) 2003 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2006: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2005: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2004: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2003: ¥1,500,000 (Direct Cost: ¥1,500,000)
KeywordsFriedel-Crafts reaction / vinylepoxide / 7-endo cyclization / hvdro-2-benzazenine / seven-membered carbocycle / seven-membered cyclic amine / stereoselective / montanine / Montanine / 合成研究 / 10員環アミナール / 環拡大反応 / 2-benzazepine / Friedel-Crafts環化 / 2-ベンザゼピン / 分子内フリーデルクラフツ反応 / エステル基 / 立体反転
Research Abstract

Nature abounds with compounds containing seven-membered carbocycles as prominent structure features. An intramolecular Friedel-Crafts reaction of epoxide can be applied to the construction of seven-membered carbocycles. Distinct from other functional groups, epoxide has two reacting point. Consequently, regioselectivity is an important issue in this reaction. It should be noted that 7-endo cyclization by intramolecular Friedel-Crafts reaction is generally difficult because 6-exo cyclization proceeds preferentially. Thus author carried out an intramolecular Friedel-Crafts cyclization of vinylepoxide. As a result, endo cyclization has been found to proceed selectively to give seven-membered ring compounds in high yields.
This procedure has also been applied to the stereo- and regioselective construction of a polyfunctional hydro-2-benzazepine and hydro-2-benzazocine. Selection of Lewis acids was found to be important. TMSOTf promotes 7-endo cyclization to give polyfunctional hydro-2-benzazepines in high yields. On the other hand, the treatment of vinylepoxides with BF_3-Et_2O resulted in the selective formation of an aminal products. The aminal formation was also applied to a ring expansion yielding 10-membered cyclic amine derivative.
Furthermore, the synthetic study of montanine, which is alkaloid containing hydrobenzazepine skeleton, was carried out. As a result, its complete skeleton has been successfully constructed.

Report

(5 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (14 results)

All 2007 2006 2003 2002 Other

All Journal Article (12 results) Publications (2 results)

  • [Journal Article] Facile Synthesis of Medium-Sized Cyclic Amines Based on Friedel-Crafts Reaction via Iminium Cation by Use of Acetylene Dicobalt Complex2007

    • Author(s)
      M.Mizukami, H.Saito, T.Higuchi, M.Imai, H.Bando, N.Kawahara, S.Nagumo
    • Journal Title

      Tetrahedron Letters 48

      Pages: 7228-7231

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Novel Construction of Hydro-2benzazepines Based on 7-endo Selective Friedel-Crafts-type Reaction of Vinyloxiranes2007

    • Author(s)
      S.Nagumo, M.Mizukami, K.Wada, T.Miura, H.Bando, N.Kawahara, Y.Hashimoto, M.Miyashita, H.Akita
    • Journal Title

      Tetrahedron Letters 48

      Pages: 8558-8561

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Facile Synthesis of Medium-Sized Cyclic Amines Based on Friedel-Crafts Reaction via Iminium Cation by Use of Acetylene Dicobalt Complex2007

    • Author(s)
      M., Mizukami, H., Saito, T., Higuchi, M., Imai, H., Bando, N., Kawahara, S., Nagumo
    • Journal Title

      Tetrahedron Letters 48

      Pages: 7228-7231

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Novel Construction of Hydro-2benzazepines Based on 7-endo Selective Friedel-Crafts-type Reaction of Vinyloxiranes2007

    • Author(s)
      S., Nagumo, M., Mizukami, K., Wada, T., Miura, H., Bando, N., Kawahara, Y., Hashimoto, M., Miyashita, H., Akita
    • Journal Title

      Tetrahedron Letters 48

      Pages: 8558-85611

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Nitrile-Promoted Rh-Catalyzed Intermo Iecular Hydroacylation of 01efins with Salicylaldehyde2007

    • Author(s)
      M.Imai, M.Tanaka, S.Nagumo, N Kawahara, H.Suemune
    • Journal Title

      Journal of Organic Chemistry 72(7)

      Pages: 2543-2546

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Synthetic Study of Tautomycin.Part 2:Synthesis of Ichihara's Fragment Based on Regioselective Enzymatic Acetylation of Complex Molecule2006

    • Author(s)
      Y.Ishii, S.Nagumo, T.Arai, M.Akuzawa, N.Kawahara, H.Akita
    • Journal Title

      Tetrahedron 62

      Pages: 716-725

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthetic Study of Tautomycin. Part 2 : Synthesis of Ichihara's Fragment Based on Regioselective Enzymatic Acetylation of Complex Molecule2006

    • Author(s)
      Y., Ishii, S., Nagumo, T., Arai, M., Akuzawa, N., Kawahara, H., Akita
    • Journal Title

      Tetrahedron 62

      Pages: 716-725

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Synthetic study of tautomycin. Part 2 : Synthesis of Ichihara' s fragment - based on regioselective enzymatic acetylation of complex molecule2006

    • Author(s)
      Ishii, H., Nagumo, S., Arai, T., Akuzawa, M., Kawahara, N., Akita, H.
    • Journal Title

      Tetrahedron 62

      Pages: 716-725

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Stereoselective Syntheses of 2,5-Disubstituted Hydroxyfuran Derivatives as Synthon of Polyether Antibiotics2003

    • Author(s)
      S.Nagumo, Y.Ishii, S.Kanno, N.Kawahara
    • Journal Title

      Heterocycles 59

      Pages: 101-105

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Stereoselective Syntheses of 2, 5-Disubstituted Hydroxyfuran Derivatives as Synthon of Polyether Antibiotics2003

    • Author(s)
      S., Nagumo, Y., Ishii, S., Kanno, N., Kawahara
    • Journal Title

      Heterocycles 59

      Pages: 101-105

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Novel Ether-ring Transformation of via a Phenonium Ion2002

    • Author(s)
      S., Nagumo, Y., Ishii, Y., Kakimoto, N., Kawahara
    • Journal Title

      Tetrahedron Letters 43

      Pages: 5333-5337

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] 「研究成果報告書概要(欧文)」より2002

    • Author(s)
      S., Nagumo, I., Miyoshi, H., Akita, N., Kawahara
    • Journal Title

      Tetrahedron Letters 43

      Pages: 2223-2226

    • Related Report
      2006 Final Research Report Summary
  • [Publications] Shinji Nagumo, Yusuke Ishii, Shinya Kanno, Norio Kawahara: "Stereoselective Syntheses of 2,5-Disubstituted Hydroxyfuran Derivatives as Synthon of Polyether Antibiotics"Heterocycles. 59・1. 101-105 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] Masanori Imai, Masakazu Tanaka, Shinji Nagumo et al.: "Double-Chelation-Assisted Rh-Catalyzed Intermolecular Hydroacylation Between Salicylaldehydes and 1,4-penta- or 1,5-hexadienes"J.Org.Chem.. 69・4. 1144-1150 (2004)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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