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Development of Efficient Functionalization Using Organozirconium and Organoselenium Compouds

Research Project

Project/Area Number 09650952
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Synthetic chemistry
Research InstitutionKanazawa University

Principal Investigator

SEGI Masahiko  Kanazawa University、Faculty of Engineering、Associate Professor, 工学部, 助教授 (90135046)

Co-Investigator(Kenkyū-buntansha) HONDA Mitsunori  Kanazawa University、Faculty of Engineering、Assistant Professor, 工学部, 助手 (60242533)
NAKAJIMA Tadashi  Kanazawa University、Faculty of Engineering、Professor, 工学部, 教授 (70019735)
Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1998: ¥1,000,000 (Direct Cost: ¥1,000,000)
KeywordsEarly Transition Metal / Phenylseleno Group / Hydrozirconation / Vinylcuprate / Conjugate Addition / [2,3]Sigmatropic Rearrangement / Selenoxide Elimination / アリルアルコール / ジルコナシクロペンテン / ビニルセレニド / アレン / ポリエン化合物 / 立体配座異性体
Research Abstract

Organozirconium compounds are useful for organic synthesis by utilizing the reactivity 01 zirconium-carbon bond with a variety of electrophilic reagents to give desired organic molecules. On the other hand, organoselenium chemistry became a very powerful tool in organic synthesis in recent times. Of perticular importance is the phenylseleno (PhSe) group owing to its easily handled nature. One of the most common and useful transformations of this group is its oxidative removal leading to olefins or allylic alcohols via selenoxide elimination or [2,3] sigmatropic rearrangement, respectively.
Zirconacyclopentenes (1) are easily prepared by coupling reaction of a low valent zirconocene with alkynes. The reaction of 1 with PhSeBr followed by proton quenching gave vinylselenides in good yields regioselectively. These compounds were oxidized to give the corresponding allene derivatives in good yields via selenoxide elimination. On the other hand, hydrozirconation of terminal alkynes having a phenylseleno group at alpha or beta position with Cp2ZrHCI (Schwartz reagent) gave the corresponding terminal vinylzirconocene derivatives regio- and stereoselectively. These vinylzirconium compounds reacted with a higher order cuprate to generate vinylcuprate intermediates via Zr-Cu transmetalation, which in the presence of electrophiles such as enones, epoxides, or benzyl bromide underwent the coupling reaction with them effectively to afford the adducts in good yields. The adducts with a phenylseleno group were oxidized with excess amounts of H202 to yield the desired products having allylic alcohol or F-shaped conjugated diene moiety in high yields via [2,3] sigmatropic rearrangement or selenoxide syn elimination, respectively.

Report

(3 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • Research Products

    (16 results)

All Other

All Publications (16 results)

  • [Publications] Guang Ming Li: "Synthesis and Structure of Some Telluroamides and Selenoamides.The First Crystallographic Study of Telluroamides." Organometallics. 16. 756-762 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Masahito Segi: "Reaction of Selenocarbonyl Compounds with Oxygen-functionalized Conjugated Dienes." Phosphorus,Sulfur,and Silicon and the Related Elements. 136. 599-602 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Guang Ming Li: "[4+2] Dimerization and Cycloaddition Reactions of α,β-Unsaturated Selenoaldehydes and Slenoletones." Journal of the Organic Chemistry. 64. 1565-1575 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Masahito Segi: "Regioselective Carbon-Selenium Bond Forming Reaction of Zirconacycles with Phenylselenenyl Halides." Tetrahedron Letters. 印刷中.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Masahito Segi: "Conjugate Addition of Vinylic Organocuprates Generated via Transmetalation of PhSe-Substituted Vinylzirconates." Tetrahedron Letters. 印刷中.

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Guang Ming Li, et al.: "Synthesis and Structure of Some Telluroamides and Selenoamides. The First Crystallographic Study of Telluroamides." Organometallics. 16. 756-762 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Masahito Segi, et al.: "Reaction of Selenocarbonyl Compounds with Oxygen-functionalized Conjugated Dienes." Phosphorus, Sulfur, and Silicon and the Related Elements. 136. 599-602 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Guang Ming Li, et al.: "[4+2]Dimerization and Cycloaddition Reactions of alpha, beta-Unsaturated Selenoaldehydes and Selenoletones." Journal of the Organic Chemistry. 64. 1565-1575 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Masahito Segi, et al.: "Regioselective Carbon-Selenium Bond Forming Reaction of Zirconacycles with Phenylselenenyl Halides." Tetrahedron Letters. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Masahito Segi, et al.: "Conjugate Addition of Vinylic Organocuprates Generated via Transmetalation of PhSe-Substituted Vinylzirconates." Tetrahedron Letters. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Masahito Segi: "Reaction of Selenocarbonyl Compounds with Oxygen-functionalized Conjugated Dienes." Phosphorus,Sulfur,and Silicon. 136. 599-602 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Masahito Segi: "Conjugate Addition of Vinylic Organocuprates Generated via Transmetalation of PhSe-Substituted Vinylzirconates." Tetrahedron Letters. 発表予定.

    • Related Report
      1998 Annual Research Report
  • [Publications] Masahito Segi: "Regioselective Carbon-Selenium Bond Forming Reaction of Zirconacycles with Phenylselenenyl Halides." Tetrahedron Letters. 発表予定.

    • Related Report
      1998 Annual Research Report
  • [Publications] Guang Ming Li: "Synthesis and Structure of Telluroamides and Selenoamides." Organometallics. 16. 756-762 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Masahito Segi: "Reaction of Selenocarbonyl Compounds with Oxygen-functionalized Conjugated Dienes." Phosphorus,Sulfur,and Silicon. (発表予定).

    • Related Report
      1997 Annual Research Report
  • [Publications] Masahito Segi: "Regioselective Carbon-Selenium Bond Forming Reaction of Zirconacycles with Phenylselenenyl Halides." Tetrahedron Letters. (発表予定).

    • Related Report
      1997 Annual Research Report

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Published: 1998-04-01   Modified: 2016-04-21  

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