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

在这个研究项目中，我们将注意力集中在设计真正重要的合成催化剂上，以开发路易斯酸/碱活性物质，以实现高选择性的立体化学控制。即，Maruoka 研究了前所未有的螯合型五配位硼配合物和在后一种化学中，成功设计了一种新的手性二齿 Ti (IV) 配合物，可用于同时与醛羰基配位，从而可以精确区分此类对映体。羰基与烯丙基三丁基锡进行新的催化、实用的对映选择性烯丙基化，制备了（2,7-二甲基-1,8-联亚苯基二氧基）双（二甲基铝）和（蒽醌-1,8-二氧基）双（三异丙氧基钛）作为二齿路易斯。用于与羰基底物同时配位的双齿化合物的高同时配位能力。与相应的单齿试剂相比，强调了有机铝和钛试剂对羰基的作用，并通过评估 Kakuchi 使用 1,2 : 4,5-二氢戊醇的环聚合反应中酮基底物的双亲电活化来表征。应用于手性固定相并阐明稻永设计的手性稀土金属的光学拆分机制。配合物作为热力学稳定的单一活性物质，用于应用不对称转化，Uemura 通过使用金属阳离子交换蒙脱土催化剂，开发了烯烃的弗里德尔-克拉夫茨型反应和醇的氧化反应，并通过盐野谷合成了一种用于替代 DNA 碱基配对的新型核苷。金属络合，并通过超分子自组装对对苯二甲酸进行分子识别Tomooka 开发了对映选择性碳阴离子反应和对映选择性自由基反应，以实现有机锂物质的动态立体化学控制。