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

在该研究项目中，我们专注于设计真正重要的合成催化剂，以开发刘易斯酸/碱基活性物种，以实现高度选择性的立体化学控制。也就是说，马鲁卡研究了前所未有的樱桃式五角杆级硼配合物和边界路易斯酸化学。在后来的化学中，成功设计了一种新的，手性的边界Ti（IV）复合物，可以用于简单的配位来实现醛的羰基，从而允许对这种羰基的精确映射鉴别，以使新的催化性催化性地催化型催化型甲基化的甲基化分离甲基化的Alldeydeylys Alldedeydylied Alldeied Alliedied Allied dydeied。 OOI制备的（2,7-二甲基-1,8-二苯基二氧）BIS（二甲基铝）和（Anthraquinone-1,8-二氧化）BIS（三异丙氧基替坦）作为鸟类Lewis lewis lewis lewis lewis lewis lewis酸，用于同时配合carbonyl substrates。与相应的单次试剂相比，强调了鸟酸盐有机铝和钛试剂对碳的高，同时的协调能力，并通过评估几种电动反应中酮ic子材料的双电电性激活的特征。 kakuchi使用了1,2：4,5-二乙醇醇的环聚合，用于施用手性固定相，并阐明了氨基酸的光学分辨率机理。 inanaga将手性稀土金属复合物设计为热力学稳定的单个活性物种，用于应用不对称的转化。 Uemura通过使用金属阳离子交换的蒙脱石催化剂形成了烷烃的弗里德尔工艺类型反应和醇的氧化反应。 Shionoya合成了一种新型的核外侧，以通过金属络合物配对替代性DNA碱，并通过超分子自组装对邻胺 - 倾斜剂量Zn（II）-Cyclen络合物的超分子自组装进行了对苯甲酸的分子识别。 Tomooka开发了对映选择性碳水化合物反应和对映选择性自由基反应，以实现有机物种的动态立体化学控制。较少的

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。

Hiroshi Furuno: "Remarkably High Asymmetric Amplification in the Chiral Lanthanide Complex-Catalyzed Hetero-Diels-Alder Reaction : First Example of the Nonlinear Effect in ML^3 System"Organic Letters. Vol.2 No.1. 49-52 (2000)

Hiroshi 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：ML^3 系统中非线性效应的第一个例子”有机快报。