Solid State Organic Chemistry: Efficient Reactions, Remarkable Yields, and Stereoselectivity
Solid State Organic Chemistry: Efficient Reactions, Remarkable Yields, and Stereoselectivity
复制标题
固态有机化学：高效反应、显着产率和立体选择性
DOI：
10.1002/chin.199616307
复制
发表时间：
1996
期刊：
影响因子：
--
通讯作者：
F. Toda
中科院分区：
文献类型：
--
作者：
F. Toda
大多数有机反应都是在溶液中进行的。其中一个原因可能是亚里士多德的著名哲学，“No Coopora nisi Fluida”，意思是“没有溶剂就不会发生反应”。这种哲学对欧洲现代科学的发展有很大的影响。在亚里士多德的古代时期，人们没有意识到许多反应是在没有溶剂的情况下发生的。例如，许多生物反应，如食物在胃和肠中的消化，细胞如卵子和精子细胞之间的反应，以及细胞的增殖，比溶液反应更固态。尽管如此，令人感到奇怪的是，几乎所有的反应都是在溶液中进行的，即使找不到使用溶剂的特殊原因，我们已经发现相当多的反应在固态下进行得很好。在某些情况下，固态有机反应比溶液反应更有效且更有选择性地发生，因为晶体中的分子紧密且规则地排列。当需要在固态下进行更有选择性的反应时，例如主-客体化学技术是适用的。客体化合物作为其包合物晶体与手性主体化合物在固态下反应得到光学活性的反应产物。根据我们的简单原理设计了各种主体化合物。包合物晶体中虽然热反应和光化学反应都可以选择性地进行，但后者的选择性通常高于前者，高效固相反应的发生表明反应物和试剂的分子可以在固相中运动。事实上，主客体包合络合作用是通过混合固态的两种晶体而发生的。令人惊讶的是，固态络合甚至选择性地发生。例如，将消旋客体和光学活性主体在固态下混合，得到客体的一种对映体与主体的包合络合物，由此获得光学活性客体。这种有效的手性识别现象在许多包合晶体中得到了观察，并利用这种现象实现了高效的光学拆分。手性最有趣的应用
Most organic reactions havebeen studied in solu-tion. One reason for this might be Aristotle’s famous philosophy,“No Coopora nisi Fluida”, which means,“No reaction occurs in the absence of solvent.” This philosophy had a big influence on the evolution of the modern sciences in Europe. In the ancient period of Aristotle, it was not realized that many reactions occur in the absence of solvent. For example, many biological reactions, such as digestion of food in the stomach and bowels, the reaction between cells such as ovum and spermatid, and the multiplication of the cell, are more solid state than solution reactions. Neverthe-less, it is verycurious that almost all reactions are still carried out in solution, even when a special reason for the use of solvent cannot be found. We have found that quite a few reactions proceed well in the solid state. In some cases, the solid state organic reaction occurs more efficiently and more selectively than does the solution reaction, since molecules in a crystal are arranged tightly and regularly. When more selective reaction in the solid state is required, the host-guest chemistry technique, for example, is applicable. Reac-tion of the guest compound as its inclusion complex crystal with a chiral host compound in the solid state gives an optically active reaction product. Various host compounds were designed by our simple principle. Although both thermal and photochemical reactions can be carried out selectively in inclusion crystals, the selectivity of the latter reaction is usually higher than that of the former.The occurrence of efficient solidstate reactions shows that molecules of reactant and reagent can move in the solid state. In fact, host-guest inclusion complexation occurs by mixing both crystals in the solid state. Surprisingly, solid state complexation even occurs selectively. For example, mixing of race-mic guest and optically active host in the solid state gives an inclusion complex of one enantiomer of the guest with the host, fromwhich optically activeguest is obtained. Such efficient chiral recognition was observed in many inclusion crystals, and efficient optical resolution was achieved by usingthis phenom-enon. The most interesting application of chiral