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

• Project/Area Number: 13304050
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: KYOTO 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
• Project Status: Completed (Fiscal Year 2003)
• Budget Amount: ¥51,480,000 (Direct Cost: ¥39,600,000、Indirect Cost: ¥11,880,000); Fiscal Year 2003: ¥13,000,000 (Direct Cost: ¥10,000,000、Indirect Cost: ¥3,000,000); Fiscal Year 2002: ¥13,000,000 (Direct Cost: ¥10,000,000、Indirect Cost: ¥3,000,000); Fiscal Year 2001: ¥25,480,000 (Direct Cost: ¥19,600,000、Indirect Cost: ¥5,880,000)
• Keywords: Silica Gel / Supported Catalyst / Asymmetric Catalysis / Chiral Ligand / Allylsilane / Organosilicon Comound / 不斉合成 / 1,4付加反応 / ロジウム触媒 / BINAP / 固相担持

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

• [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
• [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・16. 4688-4689 (2003)
• [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. 126(in press). (2004)
• [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(in press). (2003)
• [Publications] 林 民生: "Rhodium-Catalyzed Asymmetric 1,4-Addition of Aryltitanium Reagents Generating Chiral Titanium Enolates. Isolation as Silyl Enol Ethers"J. Am. Chem. Soc.. 124. 12102-12103 (2002)
• [Publications] 吉田 和弘: "A New Type of Catalytic Tandem 1,4-Addition-Aldol Reaction Which Proceeds through an (Oxa-π-allyl)rhodium Intermediate"J. Am. Chem. Soc.. 124. 10984-10985 (2002)
• [Publications] 嶋田 豊司: "A Novel Axially Chiral 2,2'-Bipyridine N, N'-Dioxide. Its Preparation and Use for Asymmetric Allylation of Aldehydes with Allyl(trichloro)silane as a Highly Efficient Catalyst"Org. Lett.. 4. 2799-2801 (2002)
• [Publications] 嶋田 豊司: "Catalytic Asymmetric Synthesis of 1-Aryl-1,2-ethanediols from Arylacetylenes by Palladium-Catalyzed Asymmetric Hydrosilylation"J. Am. Chem. Soc.. 124. 1584-1585 (2002)
• [Publications] 林 民生: "Modification of Chiral Monodentate Phosphine Ligands (MOP) for Palladium-Catalyzed Asymmetric Hydrosilylation of Cyclic 1,3-Dienes"Adv.Synth.Catal.. 343・3. 279-283 (2001)
• [Publications] 韓 鎮旭: "Preparation of a New MOP Ligand Containing a Long-Chain Alkyl Group and Its Use for Palladium-Catalyzed Asymmetric Hydrosilylation of Cyclic 1,3-Dienes"Chem.Lett.. 10. 976-977 (2001)
• [Publications] 韓 鎮旭: "Palladium-Catalyzed Asymmetric Hydrosilylation of 4-Substituted 1-Buten-3-ynes.Catalytic Asymmetric Synthesis of Axially Chiral Allenylsilanes"J.Am.Chem.Soc.. 123・51. 12915-12916 (2001)
• [Publications] 嶋田 豊司: "Preparation of Enantiomerically Pure 2'-Substituted 2-Diphenylphosphono-1,1'-binaphthyls by Reductive Cleavage of Carbon-Phosphorus Bond in a Borane Cimplex of 2-Diphenylphosphino-2'-diphenylphosphinyl-1,1'-binaphthyl"J.Org.Chem.. 66・26. 8854-8858 (2001)
• [Publications] 嶋田 豊司: "Catalytic Asymmetric Synthesis of 1-Aryl-1,2-ethanediols from Arylacetylenes by Palladium-Catalyzed Asymmetric Hydrosilylation"J.Am.Chem.Soc.. 124・8. 1584-1585 (2002)
• [Publications] 韓 鎮旭: "Enhanced Catalytic Activity in Asymmetric Hydrosilylation of l,3-Dienes with a Palladium Catalyst Soluble in the Reaction Media"Tetrahedron : Asymmetry. 13(in press). (2002)