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2003 Fiscal Year Final Research Report Summary

Development of New Synthetic Reactions by Use of Acylzirconocene Complexes

Research Project

Project/Area Number 13672233
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) 2001 – 2003
Keywordsacylzirconocene chloride / ytterbium catalyst / α-aminoketone / acyl anion / palladium catalyst / Bronsted acid / bicyclo[3.3.0] compound / rhodium catalyst
Research Abstract

Nucleophilic reactions of acylzirconocene chloride and alkenyl zirconocene chloride complexes under a variety of catalytic conditions have been investigated. Direct access of α-amino ketone derivatives through reaction of acylzirconocene chlorides with N-benzylideneaniline derivatives in which acylzirconocene chlorides react as an "unmasked" acyl anion donor, was carried out under Yb(OTf)_3/TMSOTf-catalyzed conditions. The same above reactions were also carried out with the use of Bronsted acid as a catalyst in place of Yb(OTf)_3/TMSOTf. The operationally simple three-component reaction comprised of aldehyde, aniline and acylzirconocene chloride affords α-amino ketone derivatives essentially in the absence of a catalyst. Acylzirconocene chloride complex reacts with ω-unsaturated α,β-enones and -ynones under Pd-Me_2Zn(Me_2AlCl) catalyzed conditions to give stereoselectively bicyclo[3.3.0]compounds. The 1,4-conjugated addition of alkenylzirconocene chloride complexes to α,β-enones, α,β-enoic acid esters, and α,β-enoic acid amides can be efficiently achieved by the use of [RhCl(cod)]_2 catalyst. A high diastereoselectivity was obtained through the reaction of α,β-enoic acid amide derived from Oppolzer's sultam and 2-butenoyl chloride, while the use of Evans' chiral oxazolidinone as a chiral auxiliary in place of Oppolzer's sultam gave a poor diastereoselectivity. [RhCl(COD)]_2 (2mol%)-catalyzed reactions of alkenylzirconocene chloride complexes to N-Ts, -PO(OEt)_2 and COOR aldimine derivatives also proceeded efficiently in dioxane at room temperature to give allylic amine derivatives in excellent yields. This was the first example of the catalytic addition reactions of alkenylzirconocene chloride complexes to aldimine derivatives.

  • Research Products

    (19 results)

All Other

All Publications (19 results)

  • [Publications] Akito Kakuuchi et al.: "Yb(OTf)_3-TMSOTf-catalyzed reactions of acylzirconocene chlorides to imine"Tetrahedron Lett.. 42. 1547-1549 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yuji Hanzawa et al.: "Pd-catalyzed acylation of α,β-ynone with acylzirconocene chloride and one-pot formation of cyclopentenone derivatives"Tetrahedron Lett.. 42. 1737-1739 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yuji Hanzawa et al.: "Palladium-catalyzed reaction of acylzirconocene chloride and stereoselective formation of bicyclo[3.3.0] compounds"Org.Lett.. 4. 4061-4064 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yuji Hanzawa et al.: "Palladium-catalyzed regioselective acylation of a,b-unsaturated ketone derivatives by acylzirconocene as an acyl group donor precursor"Tetrahedron. 58. 7559-7571 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yuji Hanzawa et al.: "Copper(I)-catalyzed reaction of acylzirconocene chloride : Cross-coupling and conjugate addition"Tetrahedron. 58. 10429-10435 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Akito Kakuuchi et al.: "Formation of a-amino ketone : Yb(OTf)3/TMSOTf- and Bronsted acid-catalyzed addition of acylzirconocene chloride to imine and three-componet reaction of acylzirconocene"Eur.J.Org.Chem.. 116-122 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Akito Kakuuchi et al.: "Rh(I)-catalyzed addition of alkenylzirconocene chloride to aldimine derivatives"Tetrahedron Lett.. 44. 923-926 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Akito Kakuuchi et al.: "Rh(I)-catalyzed 1,4-addition of alkenylzirconocene chloride to electron deficient alkenes"Tetrahedron. 60. 1293-1299 (2004)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 榛澤雄二: "アシルジルコノセン錯体を求核的アシル基供与体とする炭素-炭素結合形成反応"有機合成化学協会誌. 62(印刷中). (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Yuji Hanzawa: ""Titanium and Zirconium in Organic Synthesis"Ed.by I.Marek"Wiley-VCH Verlag GmbH, D-69469 Weinheim. 30 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] A.Kakuuchi, T.Taguchi, Y.Hanzawa: "Yb(OTf)_3-TMSOTf-catalyzed reactions of acylzirconocene chlorides to imine"Tetrahedron Lett.. 42. 1547-1549 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Hanzawa, A.Kakuuchi, M.Yabe, K.Narita, N.Tabuchi, T.Taguchi: "Pd-catalyzed acylation of a,b-ynone with acylzirconocene chloride and one-pot formation of cyclopentenone derivatives"Tetrahedron Lett.. 42. 1737-1739 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Hanzawa, M.Yabe, Y.Oka, T.Taguchi: "Palladium-catalyzed reaction of acylzirconocene chloride and stereoselective formation of bicyclo [3.3.0] compounds"Org.Lett.. 4. 4061-4064 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Hanzawa, N.Tabuchi, K.Narita, A.Kakuuchi, M.Yabe, T.Taguchi: "Palladium-catalyzed regioselective acylation of α,β-unsaturated ketone derivatives by acylzirconocene as an acyl group donor precursor."Tetrahedron. 58. 7559 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Hanzawa, K.Narita, M.Yabe, T.Taguchi: "Copper(I)-catalyzed reaction of acylzirconocene chloride : Cross-coupling and conjugate addition."Tetrahedron. 58. 10429 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A.Kakuuchi, T.Taguchi, Y.Hanzawa: "Formation of a-amino ketone : Yb(OTf)3/TMSOTf-and Bronsted acid-catalyzed addition of acylzirconocene chloride to imine and three-componet reaction of acylzirconocene"Eur.J.Org.Chem.. 116 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A.Kakuuchi, T.Taguchi, Y.Hanzawa: "Rh(I)-catalyzed addition of alkenylzirconocene chloride to aldimine derivatives."Tetrahedron Lett.. 44. 923 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] A.Kakuuchi, T.Taguchi, Y.Hanzawa: "Rh(I)-catalyzed 1,4-addition of alkenylzirconocene chloride to electron deficient alkenes."Tetrahedron. 60. 1293 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] 榛澤雄二, 田口武夫: "アシルジルコノセン錯体を求核的アシル基供与体とする炭素・炭素結合形成反応"有機合成化学協会誌. 62(印刷中). (2004)

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

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Published: 2005-04-19  

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