Design of Intermolecular Interactions and Dynamic Stereochemical Control by Using Lewis Acid Base Active Species

利用路易斯酸碱活性物质进行分子间相互作用和动态立体化学控制的设计

基本信息

批准号：
10208101
负责人：
MARUOKA Keiji
金额：
$ 1.73万
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

项目摘要

In this research project, we focused our attention on the design of intermolecular interactions and the dynamic stereochemical control by the use of Lewis acid/base active species in order to achieve the highly selective stereochemical control. Namely, Maruoka studied the dynamic stereochemical control of 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. Katsuki investigated the design of intermolecular interactions and the dynamic stereochemical control by using certain chiral salen/metal complexes to apply for the development of several asymmetric catalytic reactions. For example, they successfully developed asymmetric epoxidation reaction, asymmetric cyclopropanation, and asymmetric hetero-Diels-Alder reactions under the influence of chiral salen/ruthenium catalysts. Kanemasa developed an enantioselective conjugate addition of strongly coordinated nucleophiles by the use of chiral Lewis acid catalysts. Kuwano developed catalytic asymmetric reactions by using newly designed chiral catalysts possessing flexible asymmetric reaction sites, and studied the dynamic behavior of platinum chloride/chiral bis(phosphine), TRAP in solution. Mikami investigated the asymmetric activation/deactivation strategy by using certain Ru catalysts, and established a new concept on this subject. Sasai examined the dynamic stereochemical control in several asymmetric reactions by the use of combined acid/base metal complexes such as rare-earth metals or copper/amine complexes under strong magnetic fields.

在本研究项目中，我们将注意力集中在分子间相互作用的设计和利用路易斯酸/碱活性物质的动态立体化学控制上，以实现高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配合物的动态立体化学控制和二齿路易斯酸化学。在后一种化学中，成功设计了一种新型手性二齿Ti(IV)络合物，可用于与醛羰基同时配位，从而可以精确区分此类羰基，从而实现醛与烯丙基三丁基锡的新催化、实用对映选择性烯丙基化。 Katsuki通过使用某些手性salen/金属配合物研究了分子间相互作用的设计和动态立体化学控制，以应用于多种不对称催化反应的开发。例如，他们在手性salen/钌催化剂的影响下成功开发了不对称环氧化反应、不对称环丙烷化反应和不对称杂Diels-Alder反应。 Kanemasa 通过使用手性路易斯酸催化剂开发了强配位亲核试剂的对映选择性共轭加成。 Kuwano利用新设计的具有灵活不对称反应位点的手性催化剂开发了催化不对称反应，并研究了氯化铂/手性双膦、TRAP在溶液中的动态行为。 Mikami通过使用某些Ru催化剂研究了不对称活化/失活策略，并在此主题上建立了一个新概念。 Sasai 通过在强磁场下使用组合的酸/碱金属络合物（例如稀土金属或铜/胺络合物）研究了几种不对称反应中的动态立体化学控制。