By performing the reaction under air using a suitable base, selective C-alkylation of methyl N-heteroarenes with various alcohols can be effectively achieved without using any external catalyst. Control experiments reveal that transition metal catalysts are indeed not needed in the reaction. Mechanistic studies reveal that base and air can play crucial roles, so that the reaction is in effect initiated by base-promoted aerobic oxidation of the alcohols to carbonyl intermediates, which can then catalyze the C-alkylation reaction to selectively afford the alkylated N-heteroarenes, and be regenerated and recovered to furnish the catalytic cycle. This method has obvious advantages of broad substrate scope, requiring no transition metal catalysts/ligands and inert conditions, simple operation, low cost, no transition metal residue contaminant in the products, and is thus a practical way for functionalization of the N-heteroarene compounds.

Key words: alcohols, alkylation, methyl N-heteroarenes, transition metal-free