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Studies on the Synthesis and the Application of New Functionalized Phosphines

Research Project

Project/Area Number 60550596
Research Category

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

Allocation TypeSingle-year Grants
Research Field 有機工業化学
Research InstitutionKyushu Institute of Technology

Principal Investigator

MINAMI Toru  Kyushu Institute of Technology, 工学部, 教授 (10029134)

Co-Investigator(Kenkyū-buntansha) YAMAGUCHI Masahiko  Kyushu Institute of Technology, 工学部, 助教授 (30158117)
Project Period (FY) 1985 – 1986
Project Status Completed (Fiscal Year 1986)
Budget Amount *help
¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1986: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 1985: ¥1,400,000 (Direct Cost: ¥1,400,000)
KeywordsChiral Diphosphine Ligand / trans-Bis-1,2-(Diphenylphosphino)cyclobutane / Rhodium (I) Complex / Asymmetric Hydrogenation / (2-Diethoxyphosphinylcyclobutyl)triphenylphosphonium Salt / Double Wittig Reaction / 1,2-Difunctionalized Cyclobutanes / 連続Diels-Alder反応
Research Abstract

In this project, the synthesis and the application of new functionalized phosphines were studied.
In chapter 1, oxidative coupling of <alpha> , <omega> -phosphoryl-stabilized dicarbanions with Cu <Cl_2> led to 1,2-bis(diphenylphosphinyl)cyclobutanes. The effect of the methylene numbers of <alpha> , <omega> -diphosphine oxides on the cyclization was examined. The resolution of ( <-_+> )-trans-bis-1,2-(diphenylphosphinyl)cyclobutane (abbreviated DPCB oxide) with L-(-)-dibenzoyltartaric acid gave pure (-)-DPCB oxide, which was reduced with trichlorosilane to lead to optically active (+)-trans-bis-1,2-(diphenylphosphino)cyclobutane (abbreviated DPCB). The absolute configuration of trans-DPCB was determined by X-ray analysis of its Ni <Cl_2> complex. The asymmetric hydrogenation of dehydroamino acids catalyzed by a new type of cationic rhodium (I) complex [Rh・(+)-DPCB・(1,5-COD)] <^+BF_4^-> successfully gave the hydrogenated products whose optical yields were found to be good (ca. 90% ee). A new type of bidentate ligands, (2-amino-1-phosphino)cycloalkanes were synthesized.
In chapter 2, a versatile reagent, (2-diethoxyphosphinylcyclobutyl)triphenylphosphonium salt was developed. The double Wittig reaction using this salt and various carbonyl reagents produced 1,2-bis(ylidene)cyclobutanes in good yields. The 1,2-bis(ylidene)cyclobutanes underwent sequential Diels-Alder reaction with two equiv. of various dienophiles to give functionalized polycyclic compounds.
In conclusion, these results can be said to have achieved the initially attempted subjects for this project.

Report

(1 results)
  • 1986 Final Research Report Summary
  • Research Products

    (4 results)

All Other

All Publications (4 results)

  • [Publications] Toru Minami: J.Org.Chem.51. 3572-3576 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] Toru Minami: Chem.Lett.1986. 613-616 (1986)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] MINAMI, Toru: "Synthetic Applications of the 1-Cyclobutenyltriphenylphosphonium Salt. Synthesis and Reactions of 1,2-Difunctionalized Cyclobutanes" J. Org. Chem.51. 3572-3576 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary
  • [Publications] MINAMI, Toru: "Synthesis and Resolution of a New Type of Chiral Bisphosphine Ligand, trans-Bis-1,2-(Diphenylphosphino)cyclobutane, and Asymmetric Hydrogenation Using Its Rhodium Complex" Chem. Lett.1986. 613-616 (1986)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1986 Final Research Report Summary

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

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