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1999 Fiscal Year Final Research Report Summary

Search for New Synthetic Reactions using Acylzirconocene Complex as an "Unmasked" Acyl Anion

Research Project

Project/Area Number 10672000
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionTokyo University of Pharmacy and Life Science

Principal Investigator

HANZAWA Yuji  Tokyo University of Pharmacy and Life Science, School of Pharmacy, Associate Professor, 薬学部, 助教授 (10096688)

Project Period (FY) 1998 – 1999
KeywordsEarly transition metal / Acylzirconocene complex / Catalytic reaction / Coupling reaction / Regioselective reaction / Asymmetric synthesis
Research Abstract

In our ongoing research project on new synthetic reactions using acylzirconocene complex, we have exploited enormous possibilities of acylzirconocene complex for organic synthesis. During the past term of the project we established several quite new synthetic reactions in which acylzirconocene chloride reacted with aldehyde in the presence of a stoichiometric amount of Lewis acid to give a-ketol derivatives. It is the first example that the acylzirconocene chloride reacts as an "unmasked" acyl anion. We also found a Pd-catalyzed reaction of acylzirconocene chloride with organic halides to give ketone derivatives. Moreover, in the Pd-catalyzed conditions, acylzirconocene complex adds to α, β-unsaturated ketones, regioselectively. In the 1, 2-selective addition conditions, an enantioselective addition of the "unmasked" acyl anion was achieved for the first time by the use of chiral phosphine ligand. Although the asymmetric induction (66% ee) in the present reaction is not satisfactorily high yet, we are currently continuing the research to find more effective chiral ligand for zirconium metal complex.

  • Research Products

    (13 results)

All Other

All Publications (13 results)

  • [Publications] Hanzawa, Y.: "Generation of Allylic Titanocene Derivatives from Vinyl Halides and aCp_2TiCl_2-Me_3Al Reagent System"Tetrahedron Lett.. 39. 583-586 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hanzawa, Y.: "A Cp_2TiCl_2-Al(CH_3)_3 Reagent System : An Efficient Regent for Generation of Allylic Titanocene Derivatives"Tetrahedron. 54. 11387-11398 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] HARADA, S.: "Acylzirconocene Chloriclle as am "Oninasked" Acyl Anion"Angew, Chem. Int. Ed. 37. 1696-1698 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] HANZAWA, Y.: "Palladium-catalyzed Reactions of Acylzirconocen chloride with Organic halides"Tetrahedron Lett.. 39. 6249-6252 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] HANZAWA, Y.: "Palladium-catalyzed Acylation Reactions of γΒ-Unsaturated Ketoses with Acylzirconocene chloride"Tetrahedron Lett.. 39. 8141-8144 (1998)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] HANZAWA, Y.: "Acylzironocen Chloride as an "Oninasked" Aeyl Anion : Enanticoselective 1,2-addition to γ,Β-Onsaturated Ketone Derivatives"Angew. Chem. Int. Ed.. 38. 2395-2398 (1999)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Hanzawa Y.: "Generation of Allylic Titanocene Derivatives from Vinyl Halides and a Cp2TiCl2-Me3Al"Reagent System Tetrahedron Lett.. 39. 583-586 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hanzawa Y.: "A Cp2TiCl2-AlCl3 (1 : 4) Reagent System : An Efficient Reagent for Generation of Allylic Titanocene Derivatives from Vinyl Halides, Vinyl Esters and Carboxylic Esters"Tetrahedron. 54. 11387-11398 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Harada, S.: "Acylzirconocene Chloride as an "Unmasked" Acyl Anion"Angew.Chem.Int.Ed.. 37. 1696-1698 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hanzawa Y.: "Palladium-Catalyzed Reactions of Acylzirconocene Chloride with Organic Halides"Tetrahedron Lett.. 39. 6249-6252 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hanzawa Y.: "Palladium-Catalyzed Acylation Reactions of α, β-Unsaturated Ketones with Acylzirconocene Chloride : Remarkable Control of 1, 2- and 1, 4-Selectivity by the Catalyst"Tetrahedron Lett.. 39. 8141-8144 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hanzawa Y.: "Acylzirconocene Chloride as an "Unmasked" Acyl Anion : Enantioselective 1, 2-Addition to α,β-Unsaturated Ketone Derivatives"Angew.Chem.Int.Ed.. 38. 2395-2398 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Hanzawa Y.: "Copper(I)-Catalyzed Cross-Coupling Reaction of Acylzirconocene Complexes with Allylic and/or Propargylic Halides"Tetrahedron Lett. 41. 109-112 (2000)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2001-10-23  

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