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

基本信息

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

项目摘要

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，我们将注意力集中在E物种的设计上，以便在高度选择性的立体化学控制上。可以对醛的甲基丙二酰烯丙基丙二酰脱甲酰基化的醛和烯丙基丁丁素的甲脱甲酰化。走向碳...它对应单剂试剂奖杯反应。使用非对称性转化。 ennan tioselective自由基反应，以实现动态立体化学控制有机石物种。