Construction of Asymmetric Space

“非对称空间的建构”在非对称综合中起着核心作用。研究了高效不对称空间的构建及其在设计不对称合成和催化不对称合成新方法中的应用。得到以下结果：1)设计合成了多齿手性锂酰胺和可通过螯合形成有效手性空间的手性胺。新的不对称反应，如不对称去质子化，烷基化和质子化，被开发利用这些手性碱。这些不对称反应进一步发展为催化不对称反应。2)发现了旋光性α -氨基酸衍生物经去质子化反应生成手性烯醇酯的证据。提出了“手性记忆”的新概念，并将其应用于光活性化合物的合成。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，开发了高立体选择性的糖苷化方法，使产物高收率。4)设计并合成了具有高效手性空间的手性二醚和氨基膦衍生物。结果表明，它们可用于催化有机锂和有机铜试剂的不对称共轭加成反应。5)对不对称空间的性质进行了实验和理论研究，以设计新的不对称合成。采用新型有机铜试剂和烯丙基锌配合物制备了高立体选择性加成反应。

"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.