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Synthesis of Polyfunctionalyzed Molecules Using Cooperative Interactions between Multiple Elements

Research Project

Project/Area Number 11650888
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 Masahito  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) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2000: ¥1,500,000 (Direct Cost: ¥1,500,000)
Fiscal Year 1999: ¥2,100,000 (Direct Cost: ¥2,100,000)
KeywordsHydrozirconation / Phenylseleno Group / Vinylzirconocene / Dimethyltitanocene / Selenolester / Allylic Selenide / Selenoxide Elimination / [2,3]Sigmatropic Rearrangement / オレフィン化 / アルケニルセレニド / トランスメタル化 / 高次有機銅試薬 / ジルコナシクロペンテン
Research Abstract

Terminal alkynes (1) having a PhSe group on α or β carbonn atom contain three reactive sites (C-C triple bond, terminal alkynic hydrogen atom, PhSe group). Generally, hydrometalation of terminal alkynes takes place stereospecifically to give the E-alkenic metal species which are replaced by some electrophiles such as aldehydes, epoxides, and acyl halides to construct a new carbon-carbon bond. On the other hand, organoselenium chemistry became a very powerful tool in organic synthesis in recent times. Of particular importance is the owing to its easily handled nature.
1 reacted with zirconocene-ethylene complex to give regioselectively zirconacyclopentene derivatives. Hydrozirconation of 1 with Cp_2ZrHCl followed by transmetalation with Me_2Zn gave the corresponding terminal vinylzinc intermediates regio-and stereoselectively, which underwent the coupling reaction with aldehydes to afford the allylic alcohol derivatives having a phenylseleno group. Terminal hydrogen atom of 1 was easily abstracted by n-BuLi at-78℃ to generate sp carbanion species which were effectively trapped by aldehydes on epoxides. The compounds with a phenylseleno group were oxidized with excess amounts of H_2O_2 to yield the desired products having A-shaped olefinic alcohol moiety in good yields via selenoxide syn elimination.
Methylenation of phenylselenolesters with dimethyl titanocene (Cp_2TiMe_2) gave alkenyl selenides, which were subjected to oxidation with m-CPBA to afford terminal alkynes, not to allene, via selenoxide syn elimination. On the other hand, reaction of α-phenylseleno ketones with Cp_2TiMe_2 gave a mixture of isomeric allylic selenides and the subsequent oxidation by H_2O_2 led to the formation of allylic alcohols via [2,3] sigmatropic rearrangement.

Report

(3 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • Research Products

    (14 results)

All Other

All Publications (14 results)

  • [Publications] Guang Ming Li: "[4+2] Dimerization and Cycloaddition Reactions of α,β-Unsaturated Selenoaldehydes and Selenoletones."The Journal of Organic Chemistry. 64. 1565-1575 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Shuji Tomoda: "Reversal of π-Facial Diastereoselection in the Hydride Reduction of Selenanones. Further Application of the Exterior Frontier Orbital Extension Model"Tetrahedron Letters. 41. 4597-4601 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Guang Ming Li: "On the Behavior of α,β-Unsaturated Thioaldehydes and Thioketones in the Diels-Alder Reaction"The Journal of Organic Chemistry. 65. 6601-6612 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masahito Segi: "Conjugate Addition of Vinylic Organocuprates Generated via Transmetalation of PhSe-Substituted Vinylzirconates"Tetrahedron Letters. (発表予定).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Guang Ming Li: "[4+2] Dimerization and Cycloaddition Reactions of α, β-Unsaturated Selenoaldehydes and Selenoketones."The Journal of Organic Chemistry. 64. 1565-1575 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Shuji Tomoda: "Reversal of π-Facial Diastereoselection in the Hydride Reduction of Selenanones. Further Application of the Exterior Frontier Orbital Extension Model."Tetrahedron Letters. 41. 4597-4601 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Guang Ming Li: "On the Behavior of α, β-Unsaturated Thioaldehydes and Thioketones in the Diels-Alder Reaction."The Journal of Organic Chemistry. 65. 6601-6612 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masahito Segi: "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
      2000 Final Research Report Summary
  • [Publications] Shuji Tomoda: "Reversal of π-Facial Diastereoselection in the Hydride Reduction of Selenanones Further Application of the Exterior Frontier Orbital Extension Model"Tetrahedron Letters. 41. 4597-4601 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] Guang Ming Li: "On the Behavior of α,β-Unsaturated Thioaldehydes and Thioketones in the Diels-Alder Reaction"The Journal of Organic Chemistry. 65. 6601-6612 (2000)

    • Related Report
      2000 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
      2000 Annual Research Report
  • [Publications] Masahito Segi: "[4+2]Dimerization and Cycloaddition Reactions of α,β-Unsaturated Selenoaldehydes and Selenoketones."The Journal of Organic Chemistry. 64. 1565-1575 (1999)

    • Related Report
      1999 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
      1999 Annual Research Report
  • [Publications] Shuji Tomoda: "Reversal of π-Facial Diastereoselection in the Hydride Reduction of Selenanones."Chemistry Letters. (発表予定).

    • Related Report
      1999 Annual Research Report

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Published: 1999-04-01   Modified: 2016-04-21  

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