Creation of Enantioselective Cross- Coupling Reactions in the Solid State

首先，为了发展有机固相反应，在固相中进行各种有机反应。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。醇与三烷基氯硅烷的混合反应可以有效地进行醇的硅化反应。Claisen，Thorpe和Cannizzaro反应也被发现在无溶剂条件下有效地进行。Cross-Claisen和Thorpe反应也是成功的。通过对无溶剂条件下的Thorpe反应的连续红外光谱监测，发现了反应中间体，阐明了反应机理。真实的固态反应也是有效的。例如，2-萘酚在FeCl_2催化下的固相偶联反应可以高效地进行，并以较高的产率得到其二聚体2，2 ′-二羟基-1，1 ′-联萘。而2-萘酚和1，2 -萘在固相条件下的偶联反应则生成复杂的混合物。两种不同的客体分子与主体分子的包结络合，得到由三种不同组分组成的有趣的络合物。然而，不幸的是，两种互变异构体的交叉偶联反应是不成功的。当手性主体在固态下用于这种交叉偶联反应时，可以实现对映选择性无溶剂交叉偶联反应。我们要设计一个梦幻般的反应

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