Dynamic Stereochemical Control by Using Lewis Acid Base Active Species

使用路易斯酸碱活性物质进行动态立体化学控制

• 批准号: 10208201
• 负责人: MARUOKA Keiji
• 金额: $ 50.5万
• 依托单位: KYOTO UNIVERSITY (2000-2001)Hokkaido University (1998-1999)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research on Priority Areas (B)
• 财政年份: 1998
• 资助国家: 日本
• 起止时间: 1998 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-10208201/
• 关键词: Lewis acid; base active species; pentacoordinate boron complex; bidentate metal catalyst; dynamic stereochemical control; amino acid; chiral rare-earth metal complex; montmorillonite catalyst; carbanion reaction; 不斉エポキシ化; 速度論的光学分割; ルイス酸活性種; 5配

In this research project, we focused our attention on the design of truly important synthetic catalysts for the development of Lewis acid/base active species in order to achieve the highly selective stereochemical control. Namely, Maruoka studied unprecedented chelate-type pentacoordinate boron complexes and the bidentate Lewis acid chemistry. In the latter chemistry, a new, chiral bidentate Ti (IV) complex was successfully designed and can be utilized for simultaneous coordination to aldehyde carbonyls, thereby allowing the precise enantioface discrimination of such carbonyls for a new catalytic, practical enantioselective allylation of aldehydes with allyltributyltin. Ooi prepared (2,7-dimethyl-1,8-biphenylenedioxy)bis(dimethylaluminum) and (anthraquinone-1,8-dioxy)bis(triisopropoxytitanium) as bidentate Lewis acids for the simultaneous coordination to carbonyl substrates. The high, simultaneous coordination ability of the bidentate organoaluminum and titanium reagents toward carbony … More ls is emphasized in comparison with the corresponding monodentate reagents, and characterized by evaluating the double electrophilic activation of ketonic substrates in several electrophilic reactions. Kakuchi used the ring polymerization of 1,2 : 4,5-dianhydropentitol for the application to the chiral stationary phases and the elucidation of the optical resolution mechanism of amino acids. Inanaga designed chiral rare-earth metal complexes as thermodynamically stable, single active species for applying asymmetric transformations. Uemura developed the Friedel-Crafts-type reactions of alkenes and the oxidation reactions of alcohols by using metal cation-exchanged montmorillonite catalysts. Shionoya synthesized a novel nucleoside for alternative DNA base pairing through metal complexation, and carried out the molecular recognition of terephthalic acids by supramolecular self-assembly of acridine-pendant Zn(II)-cyclen complex. Tomooka developed the enantioselective carboanion reactions and the enantioselective radical reactions for effecting the dynamic stereochemical control of organolithium species. Less

在本研究计划中，我们的注意力集中在设计真正重要的合成催化剂，用于开发刘易斯酸/碱活性物种，以实现高度选择性的立体化学控制。也就是说，丸冈研究了前所未有的螯合型五配位硼络合物和双齿刘易斯酸化学。在后者的化学，一个新的，手性双齿钛（IV）配合物被成功地设计，并可用于同时协调醛羰基，从而允许精确的对映体歧视，这种羰基的一个新的催化，实用的对映选择性烯丙基化醛与烯丙基三丁基锡。Ooi制备了（2，7-二甲基-1，8-联苯二氧基）双（二甲基铝）和（蒽醌-1，8-二氧基）双（三异丙氧基钛）作为双齿刘易斯酸用于同时配位羰基底物。双齿有机铝和钛试剂对羰基的高同时配位能力 ...更多信息 LS是强调在与相应的单齿试剂相比，其特征在于通过评估在几个亲电反应的酮底物的双亲电活化。Kakuchi将1，2：4，5-二脱水戊糖醇的环聚合应用于手性固定相，并阐明了氨基酸的光学拆分机理。Inanaga设计了手性稀土金属配合物作为化学稳定的单一活性物种，用于应用不对称转化。Uemura开发了使用金属阳离子交换蒙脱石催化剂的烯烃的Friedel-Crafts型反应和醇的氧化反应。Shionoya等人通过金属络合反应合成了一种新的核苷类DNA碱基配对，并通过Zn（II）-cyclen的超分子自组装实现了对对苯二甲酸的分子识别。Tomooka发展了对映选择性碳负离子反应和对映选择性自由基反应，以实现有机锂物种的动态立体化学控制。少

项目成果

H. Hanawa: "New Chiral Bis-Titanium(IV) Catalyst with Dibenzofuran Spacer for Catalytic Asymmetric Allylation of Aldehydes and Ketone"Adv. Synth. Cat.. Vol. 343. 57-60 (2001)

H. Hanawa：“带有二苯并呋喃间隔基的新型手性双钛（IV）催化剂，用于催化醛和酮的不对称烯丙基化”Adv。

T.Ooi: "Pentaco ordinate Organoal uminum Chemistry:Catalytic Efficiency of Me3Al in the Epoxide Cleavage with Alkynyllithiums"J.Am.Chem.Soc.. 121. 3328-3333 (1999)

T.Ooi：“五坐标有机​​铝化学：Me3Al 在炔基锂环氧化物裂解中的催化效率”J.Am.Chem.Soc.. 121. 3328-3333 (1999)

H. Furuno: "Remarkably High Asymmetric Amplification in the Chiral Lanthanide Complex-Catalyzed Hetero-Diels-Alder Reaction : First Example of the Nonlinear Effect in ML3 System"Org. Lett.. Vol. 2. 49-52 (2000)

H. Furuno：“手性镧系元素配合物催化的杂狄尔斯-阿尔德反应中的显着高不对称扩增：ML3 系统中非线性效应的第一个例子”Org。

K. Tanaka: "Synthesis of a Novel Nucleoside for Alternative DNA Base Pairing through Metal Complexation"J. Org. Chem.. Vol. 64. 5002-5003 (1999)

K. Tanaka：“通过金属络合合成用于替代 DNA 碱基配对的新型核苷”J。

K.-G. Chung: "Nickel(0)-Catalyzed Asymmetric Cross-Coupling Reactions of Allylic Compounds with Arylboronic Acid"J. Chem. Soc., Perkin Trans. 1. 15-18 (2000)

公斤。