Abstract
A catalytic synthetic strategy has been developed combining two protocols, such as, direct nucleophilic substitution of alcohols followed by X- to N- alkyl group migration (X=O, S) to access N- functionalized benzoxazolones, benzothiazolethiones, indolinone, benzoimidazolethiones, and pyridinones derivatives. Methyl trifluoromethanesulfonate (MeOTf) was found to catalyze the reaction, which revealed the catalytic property of MeOTf. A mechanism was established through experiments as well as DFT calculations wherein the -OH group of alcohols were converted to the corresponding -OMe groups and in situ generated TfOH. The -OMe groups produced underwent TfOH catalyzed -X alkylation (X=O, S) of the heterocycles followed by -X- to -N- alkyl group migrations in a single step.