Abstract：
Alkylation of nitroarenes via Vicarious Nucleophilic Substitution (VNS) was tested experimentally and modelled with DFT calculations. Mechanistic studies reveal intrinsic differences between reactions of archetypal carbanion precursor PhSO2 CH2 Cl, and alkyl phenyl sulfones, in which benzenesulfinate acts as a leaving group. Accordingly, for the latter precursors steric hindrance develops at the β-elimination step, that raises energy barrier and results in the formation of byproducts.
摘要：
通过替代亲核取代（VNS）对硝基芳烃的烷基化进行了实验测试，并用DFT计算进行了建模。机理研究揭示了原型碳负离子前体PhSO2CH2Cl的反应之间的内在差异，和烷基苯砜，其中苯亚磺酸酯作为离去基团。因此，对于后者的前体，在β-消除步骤产生空间位阻，这提高了能量屏障并导致副产物的形成。
