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2003 Fiscal Year Final Research Report Summary

Development of Silica-Supported Chiral Transition Metal Catalysts and Their Application to Asymmetric Catalysis

Research Project

Project/Area Number 13304050
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

HAYASHI Tamio  Kyoto University, Department of Chemistry, Professor, 大学院・理学研究科, 教授 (00093295)

Co-Investigator(Kenkyū-buntansha) SHIMADA Toyoshi  Kyoto university, Department of Chemistry, Lecturer, 大学院・理学研究科, 講師 (20303802)
Project Period (FY) 2001 – 2003
KeywordsSilica Gel / Supported Catalyst / Asymmetric Catalysis / Chiral Ligand / Allylsilane / Organosilicon Comound
Research Abstract

We found that treatment of (allyl) organosilanes with silica gel in refluxing toluene brought about deallylation forming Si-O-Si bond with the silicon on the silica gel.This Si-O-Si bond formation provides us with a new reliable method for the functionalization of silica gel surface. Contrary to the conventional organosilicon compounds used for the modification, which are mostly those containing an alkoxy leaving group (R_nSiX_<4-n>: X=OR'), the allylsilanes can be handled under hydrolytic conditions and can be purified by silica gel chromatography if necessary. Regardless of their such stability, deallylation on the allylsilane takes place at the high temperature. This allylsilane method was applied to the immobilization of chiral phosphine ligands on silica gel surface and they were used for rhodium-catalyzed hydrogenation and palladium-catalyzed asymmetric allylic alkylation to show high enantioselectivity. The silica-supported chiral catalysts were recovered and reused for the next run. We are now in a position to immobilize various types of organic molecules on the silica support.
We have also succeeded in developing new catalytic asymmetric reactions including rhodium-catalyzed asymmetric 1,4-addition and palladium-catalyzed asymmetric hydrosilylation of olefins.

  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] 嶋田 豊司: "Functionalization on Silica Gel with Allylsilanes. A New Method of Covalent Attachment of Organic Functional Groups on Silica Gel"J.Am.Chem.Soc.. 125. 4688-4689 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 林 民生: "A Chiral Chelating Diene as a New Type of Chiral Ligand for Transition Metal Catalysts : Its Preparation and Use for the Rhodium-Catalyzed Asymmetric 1,4-Addition"J.Am.Chem.Soc.. 125. 11508-11509 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 徳永 礼仁: "Mechanistic Studies on the Catalytic Cycle of Rhodium-Catalyzed Asymmetric 1,4-Addition of Aryltitanate Reagents to α,β-Unsaturated Ketones"Proc.Natl.Acad.Sci.. 101. 5445-5449 (2004)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 林 民生: "Deuterium Labeling Studies Establishing Stereochemistry at the Oxypalladation Step in Wacker-Type Oxidative Cyclization of an o-Allylphenol"J.Am.Chem.Soc.. 126. 3036-3037 (2004)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 新谷 亮: "A New Entry of Nucleophiles in Rhodium-Catalyzed Asymmetric 1,4-Addition Reactions : Addition of Organozinc Reagents for the Synthesis of 2-Aryl-4-Piperidones"J.Am.Chem.Soc.. 126. 6240-6241 (2004)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] 青木 和子: "Immobilization of Chiral Phosphine Ligands on Silica Gel by Means of the Allylsilane Method and Their Use for Catalytic Asymmetric Reactions"Tetrahedron Asymmetry. (in press). (2004)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Toyoshi Shimada: "Functionalization on Silica Gel with Allylsilanes. A New Method of Covalent Attachment of Organic Functional Group on Silica Gel"J.Am.Chem.Soc.. 125. 4688-4689 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Tamio Hayashi: "A Chiral Chelating Diene as a New Type of Chiral Ligand for Transition Metal Catalysts: Its Preparation and Use for the Rhodium-Catalyzed Asymmetric 1,4-Addition"J.Am.Chem.Soc.. 125. 11508-11509 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Norihito Tokunaga: "Mechanistic Studies on the Catalytic Cycle of Rhodium-Catalyzed Asymmetric 1,4-Addition of Aryltitanate Reagents to α, β-Unsaturated Ketones"Proc.Natl.Acad.Sci.. 101. 5445-5449 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Tamio Hayashi: "Deuterium Labeling Studies Establishing Stereochemistry at the Oxypalladation Step in Wacker-Type Oxidative Cyclization of an 0-Allylphenol"J.Am.Chem.Soc.. 126. 3036-3037 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Ryo Shintani: "A New Entry of Nucleophiles in Rhodium-Catalyzed Asymmetric 1,4-Addition Reactions: Addition of Organozinc Reagents for the Synthesis of 2-Aryl-4Piperidones"J.Am.Chem.Soc.. 126. 6240-6241 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Kazuko Aoki: "Immobilization of Chiral Phosphine Ligands on Silica Gei by Means of the Allylsilane Method and Their Use for Catalytic Asymmetric Reactions"Tetrahedron Asymmetry. (in press).

    • 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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