Regioselective N-Functionalization of Tautomerizable Heterocycles through Methyl Trifluoromethanesulfonate-Catalyzed Substitution of Alcohols and Alkyl Group Migrations

• Autor(a) principal: Duari, Surajit
• Data de Publicação: 2022
• Outros Autores: Biswas, Subrata, Roy, Arnab, Maity, Srabani, Mishra, Abhishek Kumar, de Souza, Aguinaldo R. [UNESP], Elsharif, Asma M., Morgon, Nelson H., Biswas, Srijit
• Tipo de documento: Artigo
• Idioma: eng
• Título da fonte: Repositório Institucional da UNESP
• Texto Completo: http://dx.doi.org/10.1002/adsc.202101196; http://hdl.handle.net/11449/231595
• topic: Alcohols; Alkylation; Heterocycles; MeOTf Catalyst; Nucleophilic Substitution; Rearrangement

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. (Figure presented.).