The dimethylchloronium salt [Me2 Cl][Al(OTeF5 )4 ] is used to methylate electron-deficient aromatic systems in Friedel-Crafts type reactions as shown by the synthesis of N-methylated cations, such as [MeNC5 F5 ]+ , [MeNC5 F4 I]+ , and [MeN3 C3 F3 ]+ . To gain a better understanding of such fundamental Friedel-Crafts reactions, the role of the dimethylchloronium cation has been evaluated by quantum-chemical calculations.
Keywords: electrophilic substitution; halonium ions; methylation; reaction mechanism; weakly coordinating anion.
© 2020 The Authors. Published by Wiley-VCH GmbH.