Olah George A, Klumpp Douglas A
Loker Hydrocarbon Institute and Department of Chemistry, University of Southern California, University Park, Los Angeles, California 90089, USA.
Acc Chem Res. 2004 Apr;37(4):211-20. doi: 10.1021/ar020102p.
Nucleophilic solvation is the interaction of electron-donor solvents with electron-deficient reagents. Electrophilic solvation is the related reverse interaction. Superelectrophilic solvation involves the interaction of electron-donating groups (ligands) of overall electron-deficient species (electrophiles) with strongly electron-acceptor superacids. It occurs with liquid superacids, on solid acids, and even in some enzymatic biological systems. Diminishing neighboring group participation of the electrophilic centers by the affected groups greatly enhances their electrophilic reactivities (superelectrophilic activation), resulting in unusual reactions of substantial interest. Representative examples of superelectrophilic solvation are discussed.
亲核溶剂化作用是给电子溶剂与缺电子试剂之间的相互作用。亲电溶剂化作用是与之相关的相反的相互作用。超亲电溶剂化作用涉及总体缺电子物种(亲电试剂)的给电子基团(配体)与强吸电子超酸之间的相互作用。它发生在液体超酸中、固体酸上,甚至在一些酶促生物体系中。受影响的基团对亲电中心的邻基参与作用的减弱极大地增强了它们的亲电反应活性(超亲电活化),从而导致了一些极具研究价值的异常反应。文中讨论了超亲电溶剂化作用的典型例子。