• Search Research Projects
  • Search Researchers
  • How to Use
  1. Back to previous page

Development of Amphiphilic Resin-Supported Catalysts Realizing Water-Based Organic Synthesis

Research Project

Project/Area Number 11470472
Research Category

Grant-in-Aid for Scientific Research (B).

Allocation TypeSingle-year Grants
Section一般
Research Field Chemical pharmacy
Research InstitutionInstitute for Molecular Science (2000)
Nagoya City University (1999)

Principal Investigator

UOZUMI Yasuhiro  Institute for Molecular Science, Professor, 分子科学研究所, 教授 (90201954)

Project Period (FY) 1999 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥4,200,000 (Direct Cost: ¥4,200,000)
Fiscal Year 2000: ¥4,200,000 (Direct Cost: ¥4,200,000)
Keywordsansition metal catalysts / palladium-phosphine complexes / amphiphilic solid support / organic transformation in water / PS-PEG resin / palladium catalysis / PS-PEG レジン
Research Abstract

New amphiphilic resin-supported triarylphosphines (PEP) were designed and prepared on polyethylene glycol-polystyrene graft copolymer (PEG-PS). The PEG-PS resin-supported palladium-monophosphine complex Pd(PEP) was readily prepared by treatment of PEP with an excess amount of di(m-chloro)bis(h3-allyl) dipalladium(II) ([PdCl(h3-C3H5)]2) (Pd/P > 1/1) followed by removal of unimmobilized [PdCl(h3-C3H5)]2 by washing. Palladium complexe Pd(PEP) catalyzed allylic substitution of 3-acetoxy-1,3-diphenyl-1-propene and cinnamyl acetate with various nucleophiles including 1,3-dicarbonyl compounds, amino acids, sodiumazide, and sodium sulfinate, to give quantitative yields of corres ponding allylic substituted products in water.
The hydroxycarbonylation reaction of aryl or alkenyl halides also took place in aqueous alkaline solution under an atmospheric pressure of carbon monoxide at 25 。C in the presence of 3 mol % palladium of an amphiphilic resin-supported palladium-phosphine complexe bound to a … More polyethylene glycol-polystyrene graft copolymer (PEG-PS resin) (Pd(PEP). The reaction of aryl halides gave correspond-ing benzoic acids in quantitative yields. Pd-PEP also catalyzedHeck reaction of iodobenzene with acrylic acid to give cinnamic acid in 92%yield. No organic solvent was used for the reactions and no chromatographical purification was re-quired to obtain the products. The resin-supported catalyst was recovered by filtration and reused. No loss of catalytic activity was observed during 30 runs. The cross-coupling reaction of aryl halides or allyl acetates with arylboronic acids or sodium tetraphenylborate was catalyzed in water by the Pd(PEP) catalyst. The reaction of aryl halides with arylboron reagents in the presence of 2 mol% palladium of Pd(PEP) in aqueous alkaline solution at 25 。C gave corresponding biphenyl derivatives in high yields. Pd(PEP) also catalyzed allylic arylation of allyl acetates (including 1,3-disubstituted allyl acetates and cyclic allyl acetates) with arylboron reagents in water under the similar reaction conditions to give 80-99% yield of allylarenes. Less

Report

(3 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • Research Products

    (25 results)

All Other

All Publications (25 results)

  • [Publications] 林民生: "Asymmetric Hydrosilylation of Styrenes Catalyzed by Palladium-MOP Complexes : Ligand Modification and Mechanistic Studies"J.Org.Chem.. 66. 1441-1449 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 魚住泰広: "Catalytic Asymmetric Allylic Alkylation in Water with a Recyclable Amphiphilic Resin-Supported P, N-Chelating Palladium Complex"J.Am.Chem.Soc.. 123(in press). (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 魚住泰広: "Enantioselective desymmetrization of meso-cyclic anhydrides catalyzed by hexahydro-1H-pyrrolo[1, 2-c] imidazolones"Tetrahedron Letters. 42. 411-414 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 魚住泰広: "A parallel preparation of a bicyclic N-chiral amine library and its use for chiral catalyst screening"Tetrahedron Letters. 42. 407-410 (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 林民生: "Modification of Chiral Monodentate Phosphine (MOP) Ligands for Palladium-Catalyzed Asymmetric Hydrosilylation of Styrenes"Chem.Lett.. 1272-1273 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 柴富一孝: "Michael Reactions in Water Using Amphiphilic Resin-Supported Quaternary Ammonium Hydroxides"Synlett.. 11. 1643-1645 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 川面基: "Palladium-Catalyzed Asymmetric Reduction of Racemic Allylic Esters with Formic Acid : Effects of Phosphine Ligands on Isomerization of π-Allylpalladium Intermediates and Enantioselectivity"Tetrahedron. 56. 2247-2257 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 魚住泰広: "(R)-2-Diphenylphosphino-2'-methoxy-1, 1'-binaphthyl"Organic Synthesis. (in press). (2001)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Tamio Hayashi: "Asymmetric Hydrosilylation of Styrenes Catalyzed by Palladium-MOP Complexes : Ligand Modification and Mechanistic Studies"J.Org.Chem.. 66. 1441-1449 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Yasuhiro Uozumi: "Catalytic Asymmetric Allylic Alkylation in Water with a Recyclable Amphiphilic Resin-Supported P, N-Chelating Palladium Complex"J.Am.Chem.Soc.. 123, (in press). (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Yasuhiro Uozumi: "Enantioselective desymmetrization of meso-cyclic anhydrides catalyzed by hexahydro-1H-pyrrolo [1,2-c] imidazolones"Tetrahedron Letters. 42. 411-414 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Yasuhiro Uozumi: "A paralled preparation of a bicyclic N-chirai amine library and its use for chiral catalyst screeting"Tetrahedron Letters. 42. 407-410 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Tamio Hayashi: "Modification of Chiral Monodentate Phosphine (MOP) Ligands for Palladium-Catalyzed Asymmetric Hydrosilylation of Styrenes"Chem.Lett.. 1272-1273 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Kazutaka Shibatomi: "Michael Reactions in Water Using Amphiphilic Resin-Supported Quaternary Ammonium Hydroxides"Synlett.. 11. 1643-1645 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Motoi Kawatsura: "Palladium-Catalyzed Asymmetric Reduction of racemic Allylic Esters with Formic Acid : Effects of Phosphine Ligands on Isomerization of π-Allylpalladium Intermediates and Enantioselectivity"Tetrahedron. 56. 2247-2257 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Yasuhiro Uozumi: "(R)-2-Diphenylphosphino-2'-methoxy-1, 1'-binaphthyl"Organic Synthesis. (in press). (2001)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] 魚住泰広: "Enantioselective desymmetrization of meso-cyclic anhydrides catalyzed by hexahydro-lH-pyrrolo [1, 2-c] imidazolones"Tetrahedron Letters. 42. 411-414 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] 魚住泰広: "A parallel preparation of a bicyclic N-chiral amine library and its use for chiral catalyst screening"Tetrahedron Letters. 42. 407-410 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] 魚住泰広: "Modification of Chiral Monodentate Phosphine (MOP) Ligands for Palladium-Catalyzed Asymmetric Hydrosilylation of Styrenes"Chem.Lett.. 1272-1273 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 魚住泰広: "Michael Reactions in Water Using Amphiphilic Resin-Supported Quaternary Ammonium Hydroxides"Synlett.. 11. 1643-1645 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 魚住泰広: "Palladium-Catalyzed Asymmnetric Reduction of Racemic Allylic Esters with Formic Acid : Effects of Phosphine Ligands on Isomerization of π-Al1ylpalladium Intermediates and Enantioselectivity"Tetrahedron. 56. 2247-2257 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] 魚住泰広: "Design and Preparation of 3,3'-Disubstituted Boxax: New Chiral Bis(oxazoline)Ligands for Catalytic Asymmetric Wacker-Type Cyclization"J. Org. Chem.,. 64. 1620-1625 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 魚住泰広: "Cross-Coupling of Aryl Halides and Allyl Acetates with Arylboron Reagents in Water Using an Amphiphilic Resin-Supported Palladium Catalyst"J. Org. Chem.,. 64. 3384-3388 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 魚住泰広: "Hydroxycarbonylation of Aryl Halides in Water Catalysed by Amphiphilic Solid-Supported Phosphine-Palladium Complex"J. Org. Chem.,. 64. 6921-6923 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 魚住泰広: "Allylic Substitution in Water Catalyzed by Amphiphilic Resin-Supported Palladium-Phosphine Complexes"Tetrahedron. 55. 14341-14352 (1999)

    • Related Report
      1999 Annual Research Report

URL: 

Published: 2000-04-01   Modified: 2016-04-21  

Information User Guide FAQ News Terms of Use Attribution of KAKENHI

Powered by NII kakenhi