INCLUSION COMPOUNDS .17. CATALYSIS OF DECARBOXYLATION BY CYCLODEXTRINS - A MODEL REACTION FOR MECHANISM OF ENZYMES
INCLUSION COMPOUNDS .17. CATALYSIS OF DECARBOXYLATION BY CYCLODEXTRINS - A MODEL REACTION FOR MECHANISM OF ENZYMES
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DOI：
10.1021/ja01083a031
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发表时间：
1965-01-01
影响因子：
15
通讯作者：
KAMPE, W
中科院分区：
文献类型：
--
作者：
CRAMER, F;KAMPE, W
在以前的出版物中，我们已经证明环糊精包合物在溶液中是稳定的，在某些情况下可以作为催化剂进行反应。3当时我们还指出，酶催化的某些方面可以在包合催化的基础上加以理解。在这篇文章中，我们希望报告我们在脱羧反应的包合催化方面的一些工作结果。6这种催化的动力学和热力学数据在许多细节上类似于酶催化的那些;然而，这种模型的催化效率非常差于酶催化。（/）环糊精存在下羧酸脱羧的催化作用。反应机理典型的反应曲线如图1所示。反应温度必须接近60-70 ℃，否则脱羧反应产物的包合物沉淀。表1显示了所获得的分解率。原则上，有两种解释这种催化作用机理的方法。(1)这种催化作用可归因于环糊精空腔的基本性质，即醚和羟基O原子的给电子性质。6（2）反应
In previous publications we have shown that inclusion compounds of cyclodextrins are stable in solu-tion2 and react as catalysts in some cases. 3 At that time4 5we pointed out also that certain aspects of en-zyme catalysis can be understood on the basis of inclusion catalysis. In this publication we wish to re-port some results of our work on the inclusion catalysis of decarboxylation reactions. 6The kinetic and thermodynamic data of this catalysis resemble those of an enzyme catalysis in many details; the catalytic effectiveness of this model, however, is very inferior to the enzyme catalysis.(/) Catalysis of Decarboxylation of Carboxylic Acids inthe Presence of Cyclodextrin. Reaction Mechanism. A typical reaction curve is shown in Figure 1. The reaction temperature must be close to 60-70, otherwise the inclusion compounds of the decarboxylated reaction products precipitate. Table I shows the decomposition rates obtained. In principle there are two methods of interpreting the mechanism of this catalysis.(1) The catalytic effect can be attributed to the basic properties of the cyclodextrin cavity, ie, to the electron-donor proper-ties of ether and hydroxyl O atoms. 6 (2) The reaction