Direct Nucleophilic Addition versus a Single-Electron Transfer Pathway ofσH Adduct Formation in Vicarious Nucleophilic Substitution of Hydrogen
作者:Mieczysław Mąkosza、Andrzej Kwast
DOI:10.1002/ejoc.200400034
日期:2004.5
the vicarious nucleophilic substitution of hydrogen, namely direct nucleophilic addition of carbanions to nitroarenes and a two-step mechanism involving an electron-transfer process, are discussed on the basis of the existing data and results of the VNS reactions in which a radical probe — chloromethyl aryl sulfone bearing a 2,2-dimethylcyclopropyl substituent — was used as the carbanion precursor. (©
σH 加合物是氢替代亲核取代的关键中间体,即碳负离子直接亲核加成到硝基芳烃和涉及电子转移过程的两步机制,在现有的基础上讨论了形成 σH 加合物的两种机制途径。 VNS 反应的数据和结果,其中自由基探针 - 带有 2,2-二甲基环丙基取代基的氯甲基芳基砜 - 用作碳负离子前体。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)