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Design and development of monodentate chiral phosphines and their applications to asymmetric synthsese

Research Project

Project/Area Number 09470480
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionCHIBA UNIVERSITY

Principal Investigator

HAMADA Yasumasa  Chiba University, Faculty of Pharmaceutical Sciences, Professor, 薬学部, 教授 (90117846)

Project Period (FY) 1997 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥6,500,000 (Direct Cost: ¥6,500,000)
Fiscal Year 1998: ¥2,000,000 (Direct Cost: ¥2,000,000)
Fiscal Year 1997: ¥4,500,000 (Direct Cost: ¥4,500,000)
Keywordsmonodentate chiral phosphine / asymmetric allylic substitution reaction / palladium / trialkyl borates / 2-cycloalkenyl ester
Research Abstract

The transition-metal catalyzed asymmetric synthesis is one of the most expedient and environmentally benign processes and attracts attention for practical use. In addition the design and development of chiral ligands for the transition-metal catalyzed reactions are most fascinating and a challenging task. We have succeeded in the development of new monodentate chiral phosphines, (1R, 2S, 5R, 6S)-2,6-dimethyl-9-phenyl-9-phosphabicyclo[3 .3.1]nonane and its enantiomer ((+)- and(-)-9-PBNs) from commercially available 1,5-dimethyl- 1,5-cyclooctadiene in 4 or 5 steps. Utilizing 9-PBNs coordinated with palladium, enantioselective carbon-carbon bond, carbon-nitrogen bond, and carbon-oxygen bond forming reactions through asymmetric allylic substitution reactions have been investigated in detail. The allylic alkylation of 1,3-diphenyl-2- propenyl acetate with dimethyl malonate using the catalyst from bis(benzylidene)palladium and (-)- 9-PBN was found to proceed efficiently and afford the allylated product with 94 %ee in quantitative yield. Extension to nitrogen nucleophiles instead of carbon ones has been investigated. The primary and secondary amines and the sodium salts of the sulfonamides and imide showed the enantiomeric efficacy of up to 98 %ee. Furthermore, trialkyl borates were found to serve as oxygen nucleophiles for asymmetric allylic substitution reaction and afford the corresponding ethers with up to 96 %ee. As further extension of this asymmetric synthesis using 9-PBNs we have investigated reaction of 2-cycloalkenyl esters and found that 2-substituted 2- cycloalkenyl methyl carbonates are suitable substrates for asymmetric allylic substitution reaction.

Report

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

    (7 results)

All Other

All Publications (7 results)

  • [Publications] Hamada, Y., Seto, N., Ohmori, H., & Hatano, K.: "New Monodentate Chiral Phosphine, 2.6-Dimethyle-9-phenyl-9-phosphabicyclo [3.3.1] nonane (9-PBN) : Application to Asymmetric Allylic Substitution Reaction." Tetrahedron Letters. 37. 7565-7568 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hamada, Y.; Matsuura, F.; Oku, M.; Hatano, K.; Shioiri, T.: "Synthesis and Application of New Chiral Bidentate Phosphine, 2,7-Di-tert-butyl-9,9-dimethyl-4,5-bis (methylphenylphosphino) xanthene." Tetrahedron Letters. 38. 8961-8964 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hamada, Y., Seto, N., Ohmori, H., & Hatano, K.: "New Monodentate Chiral Phosphine, 2.6-Dimethyl-9-phenyl-9-phosphabicyclo[3.3.1]nonane (9-PBN) : Application to Asymmetric Allylic Substitution Reaction." Tetrahedron Letters. 37. 7565-7568 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hamada, Y. ; Matsuura, F. ; Oku, M. ; Hatano, K. ; Shioiri, T: "Synthesis and Application of New Chiral Bidentate Phosphine, 2,7-Di-tert-butyl-9,9-dimethyl-4,5-bis(methylphenylphosphino)xanthene." Tetrahedron Letters. 38. 8961-8964 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] Hamada,Y.,Seto,N.,Ohmori,H.,& Hatano,K.: "New Monodentate Chiral Phosphine,2.6-Dimethyl-9-phenyl-9-phosphabicyclo[3.3.1]nonane(9-PBN):Application to Asymmetric Allylic Substitution Reaction." Tetrahedron Letters. 37. 7565-7568 (1996)

    • Related Report
      1998 Annual Research Report
  • [Publications] Hamada,Y.;Matsuura,F.;Oku,M.;Hatano,K.;Shioiri,T.: "Synthesis and Application of New Chiral Bidentate Phosphine,2,7-Di-tert-butyl-9,9-dimethyl-4,5-bis(methylphenylphosphino)xanthene." Tetrahedron Letters. 38. 8961-8964 (1997)

    • Related Report
      1998 Annual Research Report
  • [Publications] Y、Hamada, N、Sato, H、Oumori, K、Hatano: "Hero Mono dentale Chiral Phosphine,2,6Dimethyl-9-phenyl-9-phospha bicyclo [3.3.1]nonane (9-PBN).Application to Asymmetric Allylic Substitution Reaction" Tetrahedron hetlers. 37. 7565-7568 (1996)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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