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Development of new efficient rearrangement reactions of compounds bearing consecutive hetero atoms

Research Project

Project/Area Number 15590032
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionKobe Pharmaceutical University

Principal Investigator

MIYATA Okiko  Kobe Pharmaceutical University, associate professor, 薬学部, 助教授 (90102110)

Co-Investigator(Kenkyū-buntansha) NAITO Takeaki  Kobe Pharmaceutical University, professor, 薬学部, 教授 (00068339)
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)
Keywordsoxime ether / indole / benzofuran / dienylimine / hydroximate / amino alcohol / hydra zone / arylamine / Lunarine / アルコキシアミン / ベンズアゼピン / Wittig転位反応 / Cytoxazone / アミノ酸 / エンアリールオキシアミン / Stemofuran A / Eupomatenoid 6 / Wittig転位 / シグマトロピー転位
Research Abstract

We have developed the new rearrangement reactions of compounds with the two consecutive hetero atoms for the efficient preparations of highly functionalized compounds and heterocycles.
1. The rearrangement reaction of acylenamines adjacent to a heteroatom
We have established a novel [3,3]-sigmatropic rearrangement of N-trifluoroacetyl enehydrazines for synthesis of indolines and indoles. Under the mild conditions, N-trifluoroacetyl enehydrazine having a cyclopentene ring smoothly underwent [3,3]-sigmatropic rearrangement followed by cyclization to give indolines. On the other hand, both cyclohexenyl N-trifluoroacetyl enehydrazine and acyclic N-trifluoroacetyl enehydrazine gave indoles in good yield. The rearrangement of enehydrazine carrying either an o-methoxy or an o-methyl groups gave the dienylimines. The N-trifluoromethanesulfonyl enehydrazine was converted into the rearranged product at low temperature. Similarly, we have found that [3,3]-sigmatropic rearrangement of O-aryloxime et … More hers took place smoothly during the course of trifluoroacetylation of 0-aryloxime ether at lower temperature to give the various benzofurans. Furthermore, short and practical syntheses of natural benzofurans were achieved without protection of the hydroxyl group in good overall yield.
2. The rearrangement reaction of imines adjacent to a heteroatom
We have developed imino 1,2-Wittig rearrangement of the hydroximates for the first time. The feasibility of this rearrangement is dependent upon the structure the substrates. The rearrangement of Z-hydroximates proceeded smoothly to give the 2-hydroxyoxime ether in good yield while the corresponding E-isomer gave a mixture of E-and Z-hydroxyoxime ethers. This method was applied to the asymmetric synthesis of (+)-cytoxazone.
3. The rearrangement reaction of amines adjacent to a heteroatom
We have found domino elimination-rearrangement-addition of alkoxy(arylmethyl)amines using organolithium and organomagnesium reagent. This method is suitable for the preparation of a-branched sec-arylamines. Furthermore, we have succeeded in the synthesis of cyclic compounds carrying an azepine ring widely found in biologically active compounds. Less

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

    (26 results)

All 2006 2005 2004 2003 Other

All Journal Article (24 results) Publications (2 results)

  • [Journal Article] Efficient synthesis of indoles using [3,3]-sigmatropic rearrangement of N-trifluoroacetyl enehydrazines.2006

    • Author(s)
      宮田 興子
    • Journal Title

      Tetrahedron 62・15

      Pages: 3629-3647

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Annual Research Report 2006 Final Research Report Summary
  • [Journal Article] Novel Domino elimination-rearrangement-addition reaction of N-alkoxy(arylmethyl)amines to N-alkyl arylamines.2006

    • Author(s)
      宮田 興子
    • Journal Title

      Synlett 14

      Pages: 2219-2222

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Reagent-controlled regioselective [3,3]-sigmatropic rearrangement of N-trifluoroacetyl enehydroxylamine and its synthetic application.2006

    • Author(s)
      武田 紀彦
    • Journal Title

      Synlett 20

      Pages: 3415-3418

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Efficient synthesis of indoles using [3,3]-sigmatropic rearrangement of N-trifluoroacetyl enehydrazines.2006

    • Author(s)
      Miyata, Okiko; Takeda, Norihiko; Kimura, Yasuo; Takemoto, Yoshiji; Tohnai, Norimitsu; Miyata, Mikiji; Naito, Takeaki.
    • Journal Title

      Tetrahedron 62-15

      Pages: 3629-3647

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Novel Domino elimination-rearrangement-addition reaction of N-alkoxy(arylmethyl)amines to N-alkyl arylamines.2006

    • Author(s)
      Miyata, Okiko; Ishikawa, Tatsuya; Ueda, Masafumi; Naito, Takeaki.
    • Journal Title

      Synlett 14

      Pages: 2219-2222

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Reagent-controlled regioselective [3,3]-sigmatropic rearrangement of N-trifluoroacetyl enehydroxylamine and its synthetic application.2006

    • Author(s)
      Takeda; Norihiko; Miyata, Okiko; Kitamura, Maria; Kagehira, Syunsuke, ; Naito, Takeaki.
    • Journal Title

      Synlett 20

      Pages: 3415-3418

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Novel domino elimination-rearrangement-addition of N-alkoxy(arylmethyl) amines to N-alkyl arylamines2006

    • Author(s)
      宮田 興子
    • Journal Title

      Synlett 14

      Pages: 2219-2222

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Reagent-controlled regioselective [3,3]-sigmatropic rearrangement of N-trifluoroacetyl enehydroxylamine and its synthetic application.2006

    • Author(s)
      宮田 興子
    • Journal Title

      Synlett 20

      Pages: 3415-3418

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Stereoselective synthesis of β-hydroxyphenylalanines using imino 1,2-Wittig rearrangement of hydroximates2005

    • Author(s)
      宮田 興子
    • Journal Title

      Chem. Pharm. Bull. 53・4

      Pages: 355-360

    • NAID

      10016652841

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Preparation of optically active α -hydroxy oxime ether by diastereoselective imino 1,2-Wittig rearrangement of hydroximates and its application to synthesis of (+)-cytoxazone.2005

    • Author(s)
      宮田 興子
    • Journal Title

      Tetrahedron Lett. 46・23

      Pages: 4015-4018

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Preparation of optically active a-hydroxy oxime ether by diastereoselective imino 1,2-Wittig rearrangement of hydroximates and its application to synthesis of (+)-cytoxazone.2005

    • Author(s)
      Miyata, Okiko; Hashimoto, Jun; Iba, Ryuuichi; Naito, Takeaki.
    • Journal Title

      Tetrahedron Lett. 46-23

      Pages: 4015-4018

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Stereoselective synthesis of β-hydroxyphenylalanines using imino 1,2-Wittig rearrangement of hydroximates.2005

    • Author(s)
      Miyata, Okiko; Asai, Hiroshi; Naito, Takeaki.
    • Journal Title

      Chem. Pharm. Bull. 53-4

      Pages: 355-360

    • NAID

      10016652841

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Stereoselective Synthesis of β-Hydroxyphenylalanines Using Imino 1,2-Wittig Rearrangement of Hydroximates2005

    • Author(s)
      宮田 興子
    • Journal Title

      Chem.Pharm.Bull. 53・4

      Pages: 355-360

    • NAID

      10016652841

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Preparation of Optically Active α-Hydroxy Oxime Ether by Diastereoselective Imino 1,2-Wittig Rearrangement of Hydroximates and its Application to Synthesis of (+)-Cytoxazone2005

    • Author(s)
      宮田 興子
    • Journal Title

      Tetrahedron Lett. 46・23

      Pages: 4015-4018

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Highly Effective Synthetic Methods for Substituted 2-Arylbenzofurans Using [3,3]-Sigmatropic Rearrangement : Short Syntheses of Stemofuran A and Eupomatenoid 6.2004

    • Author(s)
      宮田 興子
    • Journal Title

      Org. Lett. 6・11

      Pages: 1761-1763

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Imino 1,2-Wittig rearrangement of hydroximates and its application to synthesis of cytoxazone.2004

    • Author(s)
      宮田 興子
    • Journal Title

      Tetrahedron 60・5

      Pages: 3893-3914

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Imino 1,2-Wittig rearrangement of hydroximates and its application to synthesis of cytoxazone.2004

    • Author(s)
      Miyata, Okiko; Koizumi, Tomoko; Asai, Hiroshi; Iba, Ryuichi; Naito, Takeaki.
    • Journal Title

      Tetrahedron 60-5

      Pages: 3893-3914

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Highly Effective Synthetic Methods for Substituted 2-Arylbenzofurans Using [3,3]-Sigmatropic Rearrangement : Short Syntheses of Stemofuran A and Eupomatenoid 6.2004

    • Author(s)
      Miyata, Okiko; Takeda, Norihiko; Naito, Takeaki.
    • Journal Title

      Org. Lett. 6-11

      Pages: 1761-1763

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Imino 1,2-Wittig rearrangement of hydroximates and its application to synthesis of cytoxazone2004

    • Author(s)
      宮田 興子
    • Journal Title

      Tetrahedron 60・17

      Pages: 3893-3914

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Highly effective synthetic methods for substituted 2-arylbenzofurans using [3,3]-sigmatropic rearrangement : short syntheses of Stemofuran A and Eupomatenoid 62004

    • Author(s)
      宮田 興子
    • Journal Title

      Org.Lett. 6・11

      Pages: 1761-1763

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Efficient [3,3]-sigmatropic rearrangement accelerated by a trifluoroacetyl group : Synthesis of benzofurans under mild conditions.2003

    • Author(s)
      宮田 興子
    • Journal Title

      Org. Biomol. Chem. 1・2

      Pages: 254-256

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] A convenient route to the furopyran core of dysiherbaine.2003

    • Author(s)
      宮田 興子
    • Journal Title

      Org. Biomol. Chem. 1・5

      Pages: 772-774

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Efficient [3,3]-sigmatropic rearrangement accelerated by a trifluoroacetyl group : Synthesis of benzofurans under mild conditions.2003

    • Author(s)
      Miyata, Okiko; Takeda, Norihiko; Morikami, Yoshiaki; Naito, Takeaki.
    • Journal Title

      Org. Biomol. Chem. 1-2

      Pages: 254-256

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] A convenient route to the furopyran core of dysiherbaine.2003

    • Author(s)
      Miyata, Okiko; Iba, Ryuichi; Hashimoto, Jun; Naito, Takeaki.
    • Journal Title

      Org. Biomol. Chem. 1-5

      Pages: 772-774

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Publications] 宮田 興子: "Efficient [3,3]-sigmatropic rearrangement accelerated by trifluoroacetyl group : synthesis of benzofurans under mild conditions"Org.Biomol.Chem.. 1(2). 254-256 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] 宮田 興子: "A convenient route to the furopyran core of dysiherbaine"Org.Biomol.Chem.. 1(5). 772-774 (2003)

    • Related Report
      2003 Annual Research Report

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

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