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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Autores principales: Nakahara, Masataka, Hanaya, Kengo, Sugai, Takeshi, Higashibayashi, Shuhei
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2021
Materias:
Communications
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
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author Nakahara, Masataka
Hanaya, Kengo
Sugai, Takeshi
Higashibayashi, Shuhei
author_facet Nakahara, Masataka
Hanaya, Kengo
Sugai, Takeshi
Higashibayashi, Shuhei
author_sort Nakahara, Masataka
collection PubMed
description 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.
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spelling pubmed-81729992021-06-11 Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether Nakahara, Masataka Hanaya, Kengo Sugai, Takeshi Higashibayashi, Shuhei ChemistryOpen Communications 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. John Wiley and Sons Inc. 2021-01-19 /pmc/articles/PMC8172999/ /pubmed/33464712 http://dx.doi.org/10.1002/open.202000310 Text en © 2021 The Authors. Published by Wiley-VCH GmbH https://creativecommons.org/licenses/by-nc-nd/4.0/This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ (https://creativecommons.org/licenses/by-nc-nd/4.0/) License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Communications
Nakahara, Masataka
Hanaya, Kengo
Sugai, Takeshi
Higashibayashi, Shuhei
Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether
title Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether
title_full Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether
title_fullStr Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether
title_full_unstemmed Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether
title_short Theoretical Analysis of the Heterocyclic [4+2] Cycloaddition Between Pyridinium Ion and Enol Ether
title_sort theoretical analysis of the heterocyclic [4+2] cycloaddition between pyridinium ion and enol ether
topic Communications
url 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
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