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

二氧化硅负载手性过渡金属催化剂的研制及其在不对称催化中的应用

• 批准号: 13304050
• 负责人: HAYASHI Tamio
• 金额: $ 32.95万
• 依托单位: KYOTO UNIVERSITY
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 2001
• 资助国家: 日本
• 起止时间: 2001 至 2003
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-13304050/
• 关键词: 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

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.

我们发现，用硅胶在回流甲苯中处理（Allyl）有机硅烷，从而在硅胶上与硅与硅形成Si-O-SI键的交易赖以生成。这种Si-O-SI键形成为​​我们提供了一种新的可靠方法，可用于硅胶表面的功能化。与用于修饰的常规有机硅化合物相反，该化合物主要是含有烷基离开组的有机硅化合物（R_NSIX_ <4-n>：X =或'），在水解条件下可以处理Allylsilanes，并且可以在必要时被硅胶纯度纯化。无论它们的稳定性如何，烯丙基硅烷上的交易都在高温下进行。将这种烯丙基方法应用于硅胶表面上手性磷酸配体的固定，并用于铑催化的氢化和钯催化的不对称烯丙基烷基化以显示高映体选择性。硅胶支持的手性催化剂被回收并重复用于下一次跑步。现在，我们可以将各种类型的有机分子固定在二氧化硅支持上。我们还成功地开发了新的催化不对称反应，包括犀牛催化的不对称的1,4-添加和钯催化的氧化不良的不对称水合硅烷基。

项目成果

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).

Kazuko Aoki：“通过烯丙基硅烷方法将手性膦配体固定在二氧化硅上及其在催化不对称反应中的应用”四面体不对称性。

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)

Toyoshi Shimada：“用烯丙基硅烷对硅胶进行官能化。在硅胶上共价连接有机官能团的新方法” J.Am.Chem.Soc. 125・16 (2003)。

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)

Norihito Tokunaga：“铑催化的芳基钛酸酯试剂不对称 1,4-加成到 α, β-不饱和酮的催化循环的机理研究”Proc.Natl.Acad.Sci.. 101. 5445-5449 (2004)

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)

Kazuko Aoki：“通过烯丙基硅烷方法将手性膦配体固定在硅胶上及其在催化不对称反应中的应用”Tetrahedron Asymmetry 126（出版中）。

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)

Tamio Hayashi：“铑催化的芳基钛试剂的不对称 1,4-加成反应生成手性钛烯醇化物。作为硅基烯醇醚的分离”J. Soc. 124。12102-12103 (2002)