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CARBON-CARBON BOND FORMATION BY USE OF ORGANOZIRCONIUM COMPLEX UNDER TRANSITION-METAL CATALYST

Research Project

Project/Area Number 16590017
Research Category

Grant-in-Aid for Scientific Research (C)

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

Principal Investigator

HANZAWA YUJI  SHOWA PHAMACEUTICAL LTNIVERSITY, DEPARTMENT OF PHARMACY, PROFESSOR, 薬学部, 教授 (10096688)

Project Period (FY) 2004 – 2006
Project Status Completed (Fiscal Year 2006)
Budget Amount *help
¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2006: ¥500,000 (Direct Cost: ¥500,000)
Fiscal Year 2005: ¥700,000 (Direct Cost: ¥700,000)
Fiscal Year 2004: ¥2,500,000 (Direct Cost: ¥2,500,000)
Keywordsalkenylzirconocene / acylzirconocene / low valent zirconocene complex / transition-metal catalyst / nucleophilic reaction / bicycle cyclization / diastereoselectivity / chiral auxiliary / ニッケル / パラジウム / 触媒 / ジルコノセン-ブテン錯体 / ロジウム / ジルコノセン等価体
Research Abstract

Organozirconocene chloride complex, which is known to be a poor nucleophile, showed the enhanced nucleophilicity under transition-metal catalyzed conditions. Thus, alkenylzirconocene chloride complex reacted with α,β-unsaturated carbonyl compounds to give 1,4-addition products in the presence of Rh(I) catalyst. The reaction was extended to α,β-unsaturated compounds, which have a chiral amides auxiliary, and we found that the product was obtained in high diastereoselectivity, thus in optically pure state. Acylzirconocene chloride complex, which has been established as an acyl anion donor by us, showed further usefulness for the formation of carbocyclic compounds. Thus, the Pd-catalyzed reactions of acylzirconocene chlorides with co-alkenyl or-alkynyl α,β-enones afforded bicyclo[3.3.0]compounds, stereoselectively. Interestingly, the reaction of α,w-unsaturated compounds, which possess no α,β-enone functionality, was catalyzed by Ni catalyst to give bicylo[3.1.0] compounds.
The continuing study on the chemistry of low valent zirconocene complex, which can be generated by treating zirconocene dichloride with n-BuLi, indicated that an efficient formation of benzylic zirconocene complex by treating o-alkoxymethl styrene with low valent zirconocene. Formation of carbon-carbon bond from thus generated zirconocene complex was carried out in the presence of Cu catalyst, and thus the important intermediate for the preparation of estrone was efficiently generated by our zirconocene/metal catalyst chemistry.
Elucidations on the nucleophilic reactivity and the synthetic application of organozirconocene complex are our current very active research project, thus we continue the organozirconocene chemistry to find a new and noble carbon-carbon forming reaction.

Report

(4 results)
  • 2006 Annual Research Report   Final Research Report Summary
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • Research Products

    (23 results)

All 2007 2006 2005 2004

All Journal Article (23 results)

  • [Journal Article] Acylzirconocene chloride Formation of carbocycles by palladium-catalyzed cascade reaction2007

    • Author(s)
      Hanzawa, Y.
    • Journal Title

      Organometallic Chem. (In press)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Generation and reaction of heteroaromatic zirconocene : Synthetic application to polycyclic heterocycles2007

    • Author(s)
      Ikeuchi, Y.
    • Journal Title

      Tetrahedron Letters 48

      Pages: 2477-2480

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Acylzirconocene chloride Formation of carbocycles by palladium-catalyzed cascade reaction.2007

    • Author(s)
      Hanzawa, Y, Oka, Y Yabe, M.
    • Journal Title

      Tetrahedron Lett. (in press)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Generation and reaction of heteroaromatic zirconocene : Synthetic application to polycyclic heterocycles2007

    • Author(s)
      Ikeuchi, Y, Saitoh, T., Taguchi, T., Hanzawa, Y.
    • Journal Title

      Tetrahedron Lett. 48

      Pages: 2477-2480

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Acylzirconocene chloride : Formation of carbocycles by palladium-catalyzed cascade reaction2007

    • Author(s)
      Hanzawa, Y. et al.
    • Journal Title

      J. Organomet. Chem. (In press)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Generatin and reaction of heteroaromatic zirconocene : Synthetic application to polycyclic heterocycles2007

    • Author(s)
      Hanzawa, Y. et al.
    • Journal Title

      Tetrahedron Lett. 47

      Pages: 2477-2480

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Cyclization/acylation reactions by nickel-catalyzed reactions of 1,6-ynal and 1, 6-enyne derivatives with acylzirconocene chloride2006

    • Author(s)
      Saito, A.
    • Journal Title

      Tetrahedron Letters 47

      Pages: 2201-2204

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Cyclization/acylation reactions by nickel-catalyzed reactions of 1,6-ynal and 1,6-enyne derivatives with acylzirconocene chloride2006

    • Author(s)
      Saito, A., Oka, Y, Nozawa, Y., Hanzawa, Y.
    • Journal Title

      Tetrahedron Lett. 47

      Pages: 2201-2204

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Cyclization/acylation reactions by nickel-catalyzed reactions of 1, 6-ynal and 1, 6-enyne derivatives with acylzirconocene chloride2006

    • Author(s)
      Hanzawa, Y. et al.
    • Journal Title

      Tetrahedron Lett. 47

      Pages: 2201-2204

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Cyclization/acylation reactions by nickel-catalyzed reactions of 1,6-ynal and 1,6-enyne derivatives with acylzirconocene chloride2006

    • Author(s)
      Hanzawa, Y. et al.
    • Journal Title

      Tetrahedron Lett. 47

      Pages: 2201-2204

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Copper-catalyzed allylations of Zirconocene intermediate generated from o-al kenyl or o-alkynylbenzyl ether derivatives and zirconocene-butene complex2005

    • Author(s)
      Ikeuchi, Y.
    • Journal Title

      J. Org. Chem. 70

      Pages: 756-759

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Zirconocene-mediated and/or catalyzed unprecedented coupling reactions of al koxymethyl-substituted styrene derivatives2005

    • Author(s)
      Ikeuchi, Y.
    • Journal Title

      J. Org. Chem. 70

      Pages: 4354-4359

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Copper-catalyzed allylations of Zirconocene intermediate generated from o-alkenyl or o-alkynylbenzyl ether derivatives and zirconocene-butene complex2005

    • Author(s)
      Ikeuchi, Y, Taguchi, Hanzawa, Y.
    • Journal Title

      J. Org. Chem. 70

      Pages: 756-750

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Zirconocene-mediated and/or catalyzed unprecedented coupling reactions of alkoxymethyl-substituted styrene derivatives2005

    • Author(s)
      Ikeuchi, Y, Taguchi, Hanzawa, Y.
    • Journal Title

      J. Org. Chem. 70

      Pages: 4354-4359

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Zirconocene-Mediated and/or catalyzed Unprecedented Coupling Reactions of Alkoxymethyl-Substituted Styrene Derivatives2005

    • Author(s)
      Hanzawa, Y. et al.
    • Journal Title

      J. Org. Chem. 70

      Pages: 4354-4359

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Copper-catalyzed allylations of zirconocene intermediates generated from o-alkenyl or o-alkynylbenzyl ether derivatives and zirconocene butane complex2005

    • Author(s)
      Hanzawa, Y.et al.
    • Journal Title

      J.Org.Chem. 70

      Pages: 756-759

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Copper-catalyzed acylation of o-vinylbenzylzirconocene intermediate and synthetic application toward steroid skeleton2004

    • Author(s)
      Ikeuchi, Y.
    • Journal Title

      Tetrahedron Letters 45

      Pages: 4495-4498

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Copper-catalyzed allylation of o-vinylbenzylzirconocene intermediate2004

    • Author(s)
      Ikeuchi, Y.
    • Journal Title

      Tetrahedron Letters 45

      Pages: 3717-3720

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Copper-catalyzed acylation of o-benzylzirconocene intermediate and Synthetic application toward steroid skeleton2004

    • Author(s)
      Ikeuchi, Y., Taguchi, Hanzawa, Y.
    • Journal Title

      Tetrahedron Lett. 45

      Pages: 4495-4498

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Copper-catalyzed allylation of o-benzylzirconocene intermediate2004

    • Author(s)
      Ikeuchi, Y, Taguchi, Hanzawa, Y
    • Journal Title

      Tetrahedron Lett. 45

      Pages: 3717-3720

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2006 Final Research Report Summary
  • [Journal Article] Rhodium-catlyzed 1,4-addition of alkenylzirconocene chlorides to electron deficient alkene2004

    • Author(s)
      Hanzawa, Y.et al.
    • Journal Title

      Tetrahedron 60

      Pages: 1293-1299

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Copper-catalyzed allylation of o-vinylbenzylzirconocene intermediate2004

    • Author(s)
      Hanzawa, Y.et al.
    • Journal Title

      Tetrahedron Letters 45

      Pages: 3717-3720

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Copper-catalyzed acylations of o-vinylbenzylzirconocene intermediate and synthetic application toward steroid skeleton2004

    • Author(s)
      Hanzawa, Y.et al.
    • Journal Title

      Tetrahedron Letters 45

      Pages: 4495-4498

    • Related Report
      2004 Annual Research Report

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Published: 2004-04-01   Modified: 2016-04-21  

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