Creation of Enantioselective Cross- Coupling Reactions in the Solid State

固态对映选择性交叉偶联反应的产生

基本信息

批准号：
13640595
负责人：
TODA Fumio
金额：
$ 2.18万
依托单位：
OKAYAMA UNIVERSITY OF SCIENCE
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2002
项目状态：
已结题

项目摘要

Firstly, various organic neactions were carried out in the solid state in order to develop organic solid state reactions. When substrate and / or reagent is liquid, reaction between them was carred out under solvent-free conditions. Sililation reaction of alcohols proceeded efficriently just by mixing of alcohol and trialkylsilyl chloride. Claisen, Thorpe and Cannizzaro reactions were also found to proceed efficiently under solvent-free conditions. Cross-Claisen and Thorpe reactions were also successful. By monitoring of a solvent-free Thorpe reaction by continuous measurements of IR spectra, reaction intermediate was detected and reaction mechanism was clarified. Real solid state reaction is also effective. For example, FeCIa-catalyzed coupling reaction of 2-naphthol proceeded in the solid state very efficiently and its dimer 2, 2' -dihydroxy- 1, -binapthyl was obtained in good yield. However, coss-coupling reaction of 2-naphthol and 1, 2 -naphthalenediol in the solid state gave a complex mixture. Inclusion complexation of two different guest molecules by a host to give an interesting complex consisted of three different components. Unfortunately, however, cross-coupling reaction of the two tautomers was unsuccessful. When chiral host is used for such the cross-coupling reaction in the solid state, enantioselective solvent-free cross-coupling reaction can be accomplished. We are going to design such the dreamy reaction

首先，各种有机反应在固态下进行，以发展有机固相反应。当底物和/或试剂为液体时，它们之间的反应在无溶剂条件下进行。仅通过将醇与三烷基氯硅烷混合即可有效地进行醇的硅烷化反应。克莱森、索普和坎尼扎罗反应也被发现在无溶剂条件下有效进行。克罗斯克莱森和索普反应也取得了成功。通过连续测量红外光谱来监测无溶剂索普反应，检测到反应中间体并阐明反应机理。真正的固态反应也是有效的。例如，FeCla催化的2-萘酚的偶联反应在固态下非常有效地进行，并且以良好的收率获得了其二聚体2,2'-二羟基-1,-联萘。然而，固态的2-萘酚和1,2-萘二醇的共偶联反应产生复杂的混合物。主体对两种不同的客体分子进行包合络合，得到由三种不同组分组成的有趣的复合物。然而不幸的是，两个互变异构体的交叉偶联反应没有成功。当手性主体用于这种固态交叉偶联反应时，可以完成对映选择性的无溶剂交叉偶联反应。我们要设计这样梦幻般的反应