Catalysis of Hydrogen-Deuterium Exchange Reactions by 4-Substituted Proline Derivatives.,The Journal of Organic Chemistry

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Catalysis of Hydrogen-Deuterium Exchange Reactions by 4-Substituted Proline Derivatives.
The Journal of Organic Chemistry ( IF 3.3 ) Pub Date : 2019-01-02 00:00:00 , DOI: 10.1021/acs.joc.8b02644
Eddie L Myers ₁ , Michael J Palte , Ronald T Raines ₂

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The identification and understanding of structure–activity relationships is vital for rational catalyst design. A kinetic study of the hydrogen–deuterium exchange reaction of cyclohexanone in aqueous solution, as catalyzed by proline derivatives, has revealed valuable structure–activity relationships. In phosphate-buffered solution, cis-4-fluoroproline is more active than the trans isomer, a distinction that appears to originate from a destabilizing interaction between the fluorine atom and phosphate anion during general acid-catalyzed dehydration of the carbinolamine intermediate. trans-4-Ammoniumprolines are exceptionally active catalysts owing to favorable Coulombic interactions involving the ammonium group and the alkoxide moiety formed upon 1,2-addition of the proline derivative to the ketone. These results could be used for the optimization of proline catalysts, especially in transformations where the formation of the putative iminium ion is rate-limiting.

中文翻译：

4-取代的脯氨酸衍生物催化氢-氘交换反应。

对结构-活性关系的识别和理解对于合理的催化剂设计至关重要。对脯氨酸衍生物催化的环己酮在水溶液中氢-氘交换反应的动力学研究表明，其具有有价值的结构-活性关系。在磷酸盐缓冲溶液中，顺式-4-氟脯氨酸比反式异构体更具活性，这一区别似乎源于甲醇胺中间体的一般酸催化脱水过程中氟原子和磷酸根阴离子之间的不稳定相互作用。反式-4-铵脯氨酸是异常活性的催化剂，这是由于涉及铵基和脯氨酸衍生物与酮的1，2-加成反应形成的醇盐部分之间的良好库伦相互作用。这些结果可用于脯氨酸催化剂的优化，特别是在推定的亚胺离子的形成是限速的转化中。

更新日期：2019-01-02

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