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

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 der...

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Bibliographic Details
Published in:Advanced synthesis & catalysis 2022-02, Vol.364 (4), p.865-872
Main Authors: Duari, Surajit, Biswas, Subrata, Roy, Arnab, Maity, Srabani, Mishra, Abhishek Kumar, Souza, Aguinaldo R., Elsharif, Asma M., Morgon, Nelson H., Biswas, Srijit
Format: Article
Language:English
Subjects:
Alcohol
Alcohols
Alkylation
Heterocycles
MeOTf Catalyst
Nucleophilic Substitution
Rearrangement
Substitution reactions
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Summary: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.
ISSN:1615-4150
1615-4169
DOI:10.1002/adsc.202101196