Catalytic Asymmetric Synthesis and Reactions of Enolates

烯醇化物的催化不对称合成和反应

基本信息

批准号：
07457518
负责人：
KOGA Kenji
金额：
$ 4.54万
依托单位：
University of Tokyo
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

Enolates play a central role insynthetic organic chemistry. Studies have been carried out on the possibility of making the synthesis and reactions of lithium enolates enantioselective through the agency of chiral chelated lithium amides or their corresponding amines. Based on the analysis of these reactions, attempts have also been made to convert them catalytic as to the chiral bases used.1. Catalytic Asymmetric Deprotonation :The rate of deprotonation of carbonyl compounds by a tridentate lithium amide is reasonably slower than that by a bidentate lithium amide. Based on this new finding, catalytic asymmetric deprotonation of carbonyl compounds was realized for the first time by using a combination of a chiral bidentate amine and an achiral tridentate lithium amide.2. Catalytic Asymmetric Alkylation :The rate of alkylation of lithium enolate in the presence of a tetradentate amine is reasonably faster that that in the presence of a bidentate amine. Basedon this new finding, catalytic asymmetric alkylation of lithium enolates was realized for the first time by using a combination of a chiral tetradentate amine and an achiral bidentate amine.3. Catalytic Asymmetric Protonation :Catalytic asymmetric protonation of prochiral lithium enolates was realized in the presence of less than a stoichiometric amount of a chiral tetradentate amine in toluene by insoluble achiral proton sources such as succinimide. Mechanistic details are still under investigation.

enolates扮演着核心角色的合成有机化学。已经对通过手性螯合锂酰胺或其相应胺的代理进行对映射的合成和反应的可能性进行了研究。基于对这些反应的分析，也尝试将它们转化为所使用的手性碱的催化。1。催化不对称的去质子化：三叉酸锂酰胺的羰基化合物的去质子化速率比二酰胺酰胺的比较慢。基于这一新发现，首次使用手性二齿胺和Achiral Tridentate锂酰胺的催化不对称的甲骨化合物进行了羰基化合物的催化不对称的去质子化。2。催化不对称的烷基化：在存在四体胺的存在下锂烯醇的烷基化速率比在存在双齿胺的情况下要快得多。基于新发现，通过使用手性四位胺和Achiral Bentalate胺的组合，首次实现了锂烯醇的催化不对称烷基化。3。催化不对称质子化：在存在小于甲苯中手性四胺的催化量的催化含量的催化性锂烯醇的催化不对称质子化，这是在甲苯中的降化学计量含量小于降化学计量量，而不可溶性的肌肉质质子源（例如，糖尿病）在甲苯中实现。机械细节仍在研究中。