Department of Chemistry, Texas A&M University , College Station, Texas 77842, United States.
Org Lett. 2014 Jun 20;16(12):3268-71. doi: 10.1021/ol501283u. Epub 2014 Jun 10.
Matile et al. introduced the concept of anion-π catalysis [Angew. Chem., Int. Ed. 2013, 52, 9940; J. Am. Chem. Soc. 2014, 136, 2101], reporting naphthalene diimide (NDI)-based organocatalysts for the Kemp elimination reaction. We report computational analyses of the operative noncovalent interactions, revealing that anion-π interactions actually increase the activation barriers for some of these catalyzed reactions. We propose new catalysts that are predicted to achieve significant lowering of the activation energy through anion-π interactions.
马蒂尔等人[Angew. Chem., Int. Ed. 2013, 52, 9940; J. Am. Chem. Soc. 2014, 136, 2101]提出了阴离子-π催化的概念，报道了基于萘二酰亚胺（NDI）的有机催化剂用于 Kemp 消除反应。我们报告了对作用中非共价相互作用的计算分析，揭示了阴离子-π相互作用实际上会增加这些催化反应的一些活化能垒。我们提出了新的催化剂，预计通过阴离子-π相互作用可显著降低活化能。
