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Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether

Dearomative heterocyclic [4+2] cycloaddition between the N‐(2,4‐dinitrophenyl)pyridinium ion of nicotinamide and an enol ether was analyzed by Density Functional Theory (DFT) calculations. The calculation revealed that the reaction undergoes stepwise bond formation rather than occurring in a concert...

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Detalles Bibliográficos
Autores principales: Nakahara, Masataka, Hanaya, Kengo, Sugai, Takeshi, Higashibayashi, Shuhei
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8172999/
https://www.ncbi.nlm.nih.gov/pubmed/33464712
http://dx.doi.org/10.1002/open.202000310
Descripción
Sumario:Dearomative heterocyclic [4+2] cycloaddition between the N‐(2,4‐dinitrophenyl)pyridinium ion of nicotinamide and an enol ether was analyzed by Density Functional Theory (DFT) calculations. The calculation revealed that the reaction undergoes stepwise bond formation rather than occurring in a concerted manner. The experimental products were found to be both kinetically and thermodynamically favored. The calculated transition states and intermediate suggested that the high diastereoselectivity is derived from the electrostatic interaction between the 2‐nitro group of the pyridinium ion and the hydrogen of the enol ether.