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

点击翻译按钮获取中文摘要

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.