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

在本研究项目中，我们的重点是设计分子间的相互作用和动态立体化学控制使用的刘易斯酸/碱活性物种，以实现高选择性的立体化学控制。也就是说，Maruoka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的动态立体化学控制。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。Katsuki研究了分子间相互作用的设计和动态立体化学控制，通过使用某些手性salen/金属配合物来应用于开发几种不对称催化反应。例如，他们成功开发了在手性salen/钌催化剂影响下的不对称环氧化反应、不对称环丙烷化和不对称杂-Diels-桤木反应。Kanemasa通过使用手性刘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展了催化不对称反应，并研究了氯化铂/手性双膦（TRAP）在溶液中的动力学行为。Mikami通过使用某些Ru催化剂研究了不对称活化/失活策略，并在这一主题上建立了新的概念。Sasai研究了在强磁场下使用酸/碱金属复合物如稀土金属或铜/胺复合物在几个不对称反应中的动态立体化学控制。

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.