Construction of Asymmetric Space

非对称空间的构建

基本信息

批准号：
05234104
负责人：
KOGA Kenji
金额：
$ 61.25万
依托单位：
The University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research on Priority Areas
财政年份：
1993
资助国家：
日本
起止时间：
1993 至 1995
项目状态：
已结题

项目摘要

"Construction of Asymmetric Space" plays a central role in asymmetric synthesis. Investigations have been made on the construction of efficient asymmetric spaces and its applications to design novel methods of asymmetric synthesis and catalytic asymmetric synthesis. Following results were obtained.1) Multidentate chiral lithium amides and chiral amines that can form efficient chiral spaces by chelation were designed and synthesized. Novel asymmetric reactions, such as asymmetric deprotonation, alkylation, and protonation, were developed using these chiral bases. These asymmetric reactions were further developed to catalytic asymmetric reacation. 2) Evidences for the existence of chiral enolates from optically active alpha-amino acid derivatives by deprotonation were found. The new concept "Chiral Memory" was developed and applied to the synthsis of optically active compounds. 3) To utilize sugar derivatives as useful compounds having efficient chiral spaces, highly stereoselective glycosidation methods giving the product in high yields were developed. 4) Chiral di-ethers and amodophosphine derivatives providing efficient chiral spaces were designed and synthesized. They were proved to be useful for the catalytic asymmetric conjugate addition reactions of organolithium and organocopper reagents. 5) Experimental ant theoretical studies were made on the nature of asymmetric spaces for the purpose to deisgn novel asymmetric synthesis. Highly stereoselective addition reactions were developed using novel organocopper reagents and allylzinc complexes.

“不对称空间的构建”在不对称合成中起着核心作用。已经对有效的不对称空间的构建进行了研究及其在设计新型不对称合成和催化不对称合成方法上的应用。 1）设计并合成了可以通过螯合形成有效的手性空间的多齿手性锂酰胺和手性胺。使用这些手性碱基开发了新型的不对称反应，例如不对称的质子化，烷基化和质子化。这些不对称反应进一步发展为催化不对称反应。 2）通过去质子化发现了来自光学活性α-氨基酸衍生物的手性烯醇的证据。开发了新概念“手性记忆”并应用于光学活性化合物的合成。 3）为了利用糖衍生物作为具有有效手性空间的有用化合物，开发了高产物产物的高度立体选择性糖苷方法。 4）设计和合成了提供高效手性空间的手性二乙烷和氨二膦衍生物。事实证明，它们可用于有机矿和有机磷酸盐的催化不对称结合反应。 5）进行实验性蚂蚁理论研究是关于不对称空间的性质，目的是为了Deisgn新颖的不对称合成。使用新型的Organocopper试剂和烯丙基酶配合物开发了高度立体选择性的添加反应。