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1994 Fiscal Year Final Research Report Summary

Study of the correlation between the structure of auxiliary ligands for transition metal complexes as catalysts and the selectivity in homogeneous catalytic reactions

Research Project

Project/Area Number 04403018
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionTokyo Institute of Technology

Principal Investigator

YAMAMOTO Keiji  T.I.T., Chem.Eng., Professor, 工学部, 教授 (80025999)

Co-Investigator(Kenkyū-buntansha) DOI Takayuki  T.I.T., Chem.Eng., Assistant Professor, 工学部, 助手 (90212076)
MIYAZAWA Masahiro  T.I.T., Chem.Eng., Assistant Professor, 工学部, 助手 (70209899)
YAMADA Haruo  T.I.T., Chem.Eng., Assistant Professor, 工学部, 助手 (10175664)
TAKAHASHI Takashi  T.I.T., Chem.Eng., Associate Professor, 工学部, 助教授 (80110724)
Project Period (FY) 1992 – 1994
KeywordsRh(I)-Complex / Hydroformylation / Bite-Angle / pi-Allylpalladium / Cyclization / 1,3-Chirality transmission / Organozincate / Conjugate addition
Research Abstract

According to the proposed project, the Rh(I)-catalyzed hydroformylation, Pd(0)-catalyzed allylation reaction, and conjugate addition of various organozincates were carried out. Especially, the ligand effects on the chemo-, regio-, as well as stereoselectivity in these reactions were elucidated in terms of both steric and electronic origin. Thus, the report consists of the following items ;
1. Novel auxiliary ligands for rhodium(I) complexes and their selectivity in hydroformylation of alkenes-
With use of the chiral, chelating phsophorus ligands (L-L) having a wide bite angle (-120゚), [RhH(CO)_2L-L] exhibited high catalytic activity in the hydroformylation of vinylarenes, but with low enantioselectivity.
2. Regio- and stereoselectivity in palladium(0)-catalyzed allylation-
Pd(0)-catalyzed allylation of 2,7-octadienyl acetate gave rise to a novel five-membered ring formation which crucially relied on acetic acid as a solvent. The novel cyclization via pi-allylpalladium intermediates with stereospecific 1,3-chirality transmission was realized in certain prostaglandin synthesis.
3. Conjugate addition of functionalized organozincates and their applications to organic syntheses-
Diastereoselective addition of particular(Z)-vinylzincates to 4-alkoxy-2-cyclopentenone, followed by an enolate trapping with propargylic iodide, completed the prostaglandin synthesis.

  • Research Products

    (16 results)

All Other

All Publications (16 results)

  • [Publications] 宮澤 眞宏: "Palladium-Complex-Catalyzed Decarboxylation-Carbonylation of Allyl Diethylcarbamates" Synlett. 323-324 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 高橋 孝志: "Synthesis of Chiral Prostaglandin (PGE_2)via Stork Intermediate by using Vinylzincates for Conjugate Addition" Natural Product Letters. 1. 263-267 (1993)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 山本 經二: "New Ligand with a Wide Bite Angle.Efficient Catalytic Activity in the Rh(I)-Catalyzed Hydroformylation of Olefins" Chem.Lett.189-192 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 寺門 正彦: "A Novel Palladium(0)-Catalyzed Cyclization of 2,7-Octadieny1 Carbonate Containing an Allylsilane Moiety" Synlett. 134-136 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 宮澤 眞宏: "Palladium-Catalyzed Aminocarbonylation of CinnamylN,N-Dialkylcarbamates.An Intriguing Crossover with p-Methylcinnamylamines" Chem.Lett.491-494 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 富樫 和彦: "Chirality Transfer in the Palladium(0)-Catalyzed Cyclization of 3-Oxo-8,9-dihydroxytetradeca-1,6-diene Derivatives into 2-Methylenecyclopentanones" Tetrahedron Lett.35. 3333-3336 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 寺門 正彦: "Palladium(0)-Catalyzed Cyclization-Carbonylation of 2,7 -Octadienyl Acetate and Homologues" Tetrahedron. 50. 5705-5718 (1994)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 土井 隆行: "Chirality Transfer in Palladium Catalyzed Reactions of Allylammonium Salts" Tetrahedron:Asymmetry. 6(in press). (1995)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Masahiro MIYAZAWA: "Palladium-Complex-Catalyzed Decarboxylation-Carbonylation of Allyl Diethylcarbamates" Synlett. 323-324 (1992)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Takashi TAKAHASHI: "Synthesis of Chiral Prostaglandin(PGE_2) via Stork Intermediate by using Vinylzincates" Natural Products Letters. 1. 263-267 (1993)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kenji YAMAMOTO: "New Ligand with a Wide Bite Angle, Efficient Catalitic Activity in the Rh(I)-Catalyzed Hydroformylation of Olefins" Chem.Lett.189-192 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Masahiko TARAKADO: "A Novel Palladium(0)-Catlyzed Cyclization of 2,7-Octadienyl Carbonate" Synlett. 134-136 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Masahiro MIYAZAWA: "Palladium-Catalyzed Aminocarboxylation of Cinnamyl N,N-Dialkylcarbamates. An Intriguing Crossover with rho-Methylcinnamylamines" Chem.Lett.491-494 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuhiko TOGASHI: "Chirality Transfer in the Palladium(0)-Catalyzed Cyclization of 3-Oxo-8,9-dihydroxytetradeca-1,6-diee Derivatives into 2-Methylenecyclopentanones" Tetrahedron Lett.35. 3333-3336 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Masahiko TERAKADO: "Palladium(0)-Catalyzed Cyclization-Carbonylation of 2,7-Octadienyl Acetate and Homologues" Tetrahedron. 50. 5705-5718 (1994)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Takayuki DOI: "Chirality Transfer in Palladium Catalyzed Reactions of Allylammonium Salts." Tetrahedron : Asymmetry. 6, (in press). (1995)

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

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Published: 1996-04-15  

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