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Catalytic O ‐ to N ‐Alkyl Migratory Rearrangement: Transition Metal‐Free Direct and Tandem Routes to N ‐Alkylated Pyridones and Benzothiazolones
Author(s) -
Mishra Abhishek Kumar,
Morgon Nelson Henrique,
Sanyal Suparna,
Robinson de Souza Aguinaldo,
Biswas Srijit
Publication year - 2018
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201800664
Subject(s) - chemistry , alkyl , catalysis , alkylation , tandem , transition metal , tsuji–trost reaction , functional group , alkoxy group , leaving group , medicinal chemistry , transition state , combinatorial chemistry , organic chemistry , palladium , materials science , polymer , composite material
The present study reports the synthesis of N ‐alkylated pyridones and benzothiazolones via O ‐ to N ‐alkyl group migration under transition metal‐free TfOH‐catalyzed reaction conditions for the first time, to the best of our knowledge. Primary as well as secondary alkyl groups smoothly migrate under the present reaction conditions. Moreover, a minor modification of the protocol used in this study is found to be applicable for an entirely new tandem synthesis of 2‐alkoxy‐ N ‐heterocycles from the simplest starting materials in a solvent‐free reaction conditions. Density Functional Theory (DFT) calculation identifies the energy species associated with the rearrangement, whereas, mechanistic experiments explore the role of the catalyst as the alkyl group transfer mediator.