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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。研究了有效的不对称空间的构造及其在设计不对称合成和催化不对称合成新方法方面的应用。1)设计并合成了多齿手性锂盐和手性胺类化合物，它们可以通过络合作用形成高效的手性空间。利用这些手性碱开发了不对称去质子化、烷基化和质子化等新的不对称反应。这些不对称反应进一步发展为催化不对称反应。2)发现了光学活性α-氨基酸衍生物通过去质子化得到手性烯醇酸酯的证据。发展了“手性记忆”的新概念，并将其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高效手性空间的有用化合物，开发了高立体选择性的糖苷化方法，以获得高产率的产品。4)设计合成了提供高效手性空间的手性双醚和氨基膦类化合物。它们对有机锂和有机铜试剂的催化不对称共轭加成反应是有用的。5)对不对称空间的性质进行了实验蚂蚁理论研究，旨在设计新的不对称合成方法。利用新型有机铜试剂和烯丙基锌配合物开发了具有高度立体选择性的加成反应。