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Investigations on the Development of New Reactions and New Organic Reagents by Using High Reactivities of Heterocycles Bearing Sulfur Functional Groups

Research Project

Project/Area Number 61470019
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionUniversity of Tsukuba

Principal Investigator

FURUKAWA Naomichi  Department of Chemistry, University of Tsukuba, 化学系, 教授 (80015966)

Project Period (FY) 1986 – 1988
Project Status Completed (Fiscal Year 1988)
Budget Amount *help
¥6,300,000 (Direct Cost: ¥6,300,000)
Fiscal Year 1988: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1987: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1986: ¥3,800,000 (Direct Cost: ¥3,800,000)
KeywordsPyridyl Sulfoxides / Pyridyl Sulfones / Generation of Sulfenic Acids / Pyridyl Grignard Reagents / Optically Active Pyridyl Sulfoxides / Asymmetric Synthesis / Ligand Exchange and Ligand Coupling / σスルフラン / 複素環(ヘテロ環)スルホキシド / α-ピコリルスルホキシド / 光学活性スルホキシド / 不斉誘導 / 脱スルフィニル化 / スルホキシドのリチオ化 / キノリルスルホキシド / 複素環グリニヤール試薬 / ベンザイン / ピリザイン / グリニヤール交換反応 / イプリ置換反応 / リガンドカップリング / スルフィン酸 / スルフェン酸
Research Abstract

1. Numerous organic sulfur compounds bearing pyridyl and related azaheterocycles were prepared and investigated their physical and chemical properties. Several new reactions of these compounds were found. alpha-Sulfinyl and sulfonyl-pyridines and N-oxides react readily with KOH in MeOH to afford various sulfenic and sulfinic acids. Especially, first preparation of stable sodium sulfenate was found.
2. beta- and gamma.-Pyridyl phenyl sulfoxides were found to react with alkyl Grignard reagents at the sulfinyl sulfur atom to give both beta- and gammapyridyl Grignard reagents which react further with electrophiles to provide various new pyridyl compounds. On the other hand, alpha-derivative reacts with alkyl grignard reagents to afford the corresponding alpha-phenylpyridine in good yield. These two reactions are considered to proeed via a common intermediate " -sulfurance".
3. When pyridyl sulfoxides were treated with pyridyl grignard reagents except in the reactions of gamma-pyridyl sulfoxide and gamma-PyMgBr, the corresponding both symmetric and unsymmetric bis-azaaryls were obtained in good yields. These compounds are useful for chelating agents of heavy metals and this procedures are convenient for preparation of these chelating agents.
4. alpha- beta- and gamma-pyridyl Grignard reagents were prepared from the reactions of iodobenzenes with ethyl Grignard reagent.
5. Pyridyl phenyl sulfoxides were found to react with LDA to give the corresponding alpha-lithiated sulfoxides specifically at the pyridyl ring. The lithiated sulfoxides react further with various electrophiles to be converted to the corresponding pyridyl derivatives in high yields.

Report

(4 results)
  • 1988 Annual Research Report   Final Research Report Summary
  • 1987 Annual Research Report
  • 1986 Annual Research Report
  • Research Products

    (28 results)

All Other

All Publications (28 results)

  • [Publications] N.Furukawa: Heterocycles. 24. 3019-3022 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] N.Furukawa: Tetrahedron Letters. 27. 3899-3902 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] N.Furukawa: Heterocycles. 24. 3337-3340 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] N.Furukawa: Tetrahedron Letters. 28. 2727-2730 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] N.Furukawa: Tetrahedron Letters. 28. 5845-5848 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] 古川尚道: 有機合成化学協会誌. 45. 624-639 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] S.Oae;N.Furukawa: "Advanced Heterocyclic Chemistry" John wiley and Sons, (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] N. Furukawa: "A Convenient Preparation of Sulfinic Acids by the Reaction of 2 Sulfonylpyridines and their N-Oxides with Nucleophiles" Heterocycles. 24. 3019-3022 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] N. Furukawa: "Reactions of Pyridyl and Quinolyl Sulfoxides with Grignard Reagent: A Convenient Preparation of Pyridyl and Quinolyl Grignard Reagents" Tetrahedron Letters. 27. 3899-3902 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] N. Furukawa: "Ipso Substitution Reactions of 2- and 4-Sulfonylpyridines with Grignard Reagents" Heterocycles. 24. 3337-3340 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] N. Furukawa: "A New Source for Generation of Benzyne and Pyridyne: Reactions of o-Halophenyl (or 3-Bromo-4-pyridyl) phenyl Sulfoxides with Grignard Reagents" Tetranedron Letters. 28. 2727-2730 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] N. Furukawa: "Preparation of Pyridyl Grignard Reagents and Cross--Coupling Reactions with Sulfoxides bearing azaheterocycles" Tetrahedron Letters. 28. 5845-5848 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] 古川尚道: 有機合成化学協会誌. 45. 624-639 (1987)

    • Related Report
      1988 Annual Research Report
  • [Publications] N.Furukawa: J.Org.Chem.,to be submitted.

    • Related Report
      1988 Annual Research Report
  • [Publications] N.Furukawa: J.Org.Chem.,to be submitted.

    • Related Report
      1988 Annual Research Report
  • [Publications] N.Furukawa: J.Org.Chem.

    • Related Report
      1988 Annual Research Report
  • [Publications] N.Furukawa: Tetrahedron Letters. 26. 2727-2730 (1987)

    • Related Report
      1987 Annual Research Report
  • [Publications] N.Furukawa: Tetrahedron Letters. 28. 5845-5848 (1987)

    • Related Report
      1987 Annual Research Report
  • [Publications] T.Nabeshima: Tetrahedron Letters. 28. 6211-6214 (1987)

    • Related Report
      1987 Annual Research Report
  • [Publications] S.Oae: J.Chem.Soc.Perkin II. 405-411 (1987)

    • Related Report
      1987 Annual Research Report
  • [Publications] O.Kikuchi: Bull.Chem Soc.Japan. 60. 3785-3786 (1987)

    • Related Report
      1987 Annual Research Report
  • [Publications] T.Kawai: Phosphorus and Sulfur. 34. 139-148 (1987)

    • Related Report
      1987 Annual Research Report
  • [Publications] N.Furukawa: Tetrahedron Letters. 27. 3898-3891 (1986)

    • Related Report
      1986 Annual Research Report
  • [Publications] N.Furukawa: Heterocycles. 24. 3019-3023 (1986)

    • Related Report
      1986 Annual Research Report
  • [Publications] N.Furukawa: Heterocycles. 24. 3337-3341 (1986)

    • Related Report
      1986 Annual Research Report
  • [Publications] S.Oae: J.Chem.Soc.Perkin-2. (1987)

    • Related Report
      1986 Annual Research Report
  • [Publications] N.Furkawa: Sulfur Reports. 7. 47-88 (1986)

    • Related Report
      1986 Annual Research Report
  • [Publications] 古川尚道: 有機合成化学協会誌. 45. (1987)

    • Related Report
      1986 Annual Research Report

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Published: 1987-03-31   Modified: 2016-04-21  

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