(Pre)association as a crucial step for computational prediction and analysis of the catalytic activity of σ-hole donating organocatalysts,Organic Chemistry Frontiers

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(Pre)association as a crucial step for computational prediction and analysis of the catalytic activity of σ-hole donating organocatalysts
Organic Chemistry Frontiers ( IF 4.6 ) Pub Date : 2022-11-22 , DOI: 10.1039/d2qo01648f
Denis A. Polonnikov ₁ , Mikhail V. Il'in ₁ , Yana V. Safinskaya ₁ , Irina S. Aliyarova ₁ , Alexander S. Novikov _{1,

2} , Dmitrii S. Bolotin ₁

Affiliation

Based upon the experimentally obtained kinetic data on iodonium salt catalyzed nucleophilic addition of isocyanide to imine leading to imidazopyridine species, a reliable model for DFT calculations has been suggested. It was shown that preassociation of the catalysts with the reaction species might significantly affect the total energy profile of the reaction obtained by DFT. The associates of the organocatalysts featuring the solvent molecules ligated to its σ-holes should be used as a starting point for calculations. Taking these reaction steps into consideration during the calculations leads to significantly more reliable theoretical results, which can be applied either for prediction of the catalytic activity of yet untested species or for justification of the catalytic paths based upon the experimental kinetic data as well.

中文翻译：

(Pre)association 作为计算预测和分析 σ-hole 有机催化剂催化活性的关键步骤

基于实验获得的碘盐催化异氰化物亲核加成亚胺导致咪唑并吡啶物种的动力学数据，提出了用于 DFT 计算的可靠模型。结果表明，催化剂与反应物种的预结合可能会显着影响 DFT 获得的反应的总能量分布。以溶剂分子连接到其 σ 孔上为特征的有机催化剂的缔合物应该用作计算的起点。在计算过程中考虑这些反应步骤会导致更可靠的理论结果，这些结果可用于预测尚未测试的物种的催化活性或基于实验动力学数据证明催化路径的合理性。

更新日期：2022-11-22

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