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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Theoretical Study on Acidities of (S)-Proline Amide Derivatives in DMSO and Its Implications for Organocatalysis
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Theoretical Study on Acidities of (S)-Proline Amide Derivatives in DMSO and Its Implications for Organocatalysis

机译：DMSO中（S）-脯氨酸酰胺衍生物酸度的理论研究及其对有机催化的意义

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摘要

The acidities (pK_a values) of proline amide derivatives are of great importance for understanding the catalytic activity of proline-based organocatalysts. The development of new catalysts could also benefit from the systematic study of the pK_a values of these compounds. However, only a few pKa values of the proline-based organocatalysts are currently available due to the difficulty in experimentally measurements. In this work, we set out to study the pKa values of various proline amide derivatives with theoretical calculations. Different theoretical methods were evaluated and the combined method, B3PW91/6-311++G(3df,2p)//B3LYP/6- 31+G(d)//HF//CPCM/UA0, was found to be the best one in reproducing the pK_a values of structurally unrelated amides and amide derivatives in DMSO. The MAD and RMSE of the newly developed theoretical model equal to 0.98 and 1.3 pK units, respectively. The method also enabled the systematically study on various structural effects on pK_a values of proline amide derivatives, such as the ZE-isomerization, remote substitution, and R-substitution effects, for the first time. The pK_a values of a series of chiral amides were also studied in this work. Finally, we applied the theoretical method to predict a large number of proline-based organocatalysts and established an extensive acidity scale of the compounds.
机译：脯氨酸酰胺衍生物的酸度（pK_a值）对于理解基于脯氨酸的有机催化剂的催化活性非常重要。对这些化合物的pK_a值进行系统的研究也可以开发新的催化剂。然而，由于在实验上的测量困难，目前仅基于脯氨酸的有机催化剂的几个pKa值可用。在这项工作中，我们着手通过理论计算研究各种脯氨酸酰胺衍生物的pKa值。评价了不同的理论方法，发现组合方法B3PW91 / 6-311 ++ G（3df，2p）// B3LYP / 6- 31 + G（d）// HF // CPCM / UA0是最好的一种用于复制DMSO中结构无关的酰胺和酰胺衍生物的pK_a值的方法。新开发的理论模型的MAD和RMSE分别等于0.98和1.3 pK单位。该方法还首次系统地研究了脯氨酸酰胺衍生物对pK_a值的各种结构效应，例如ZE异构化，远程取代和R取代效应。在这项工作中还研究了一系列手性酰胺的pK_a值。最后，我们应用理论方法预测了大量基于脯氨酸的有机催化剂，并建立了广泛的酸度范围。

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