Insight into the factors controlling the equilibrium of allylic azides

Several allylic azides with different double bond substitutions were studied to understand the factors, governing their equilibrium using density functional theory along with the quantum theory of atoms in molecules, non-covalent interactions and natural bond orbital approaches. The results showed t...

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Autores principales: Vallejos, Margarita M., Labadie, Guillermo Roberto
Formato: article artículo publishedVersion
Lenguaje:Inglés
Publicado: Royal Society of Chemistry 2020
Materias:
Allylic azides
Equilibrium
Regioisomer predominance
Acceso en línea:http://hdl.handle.net/2133/18277
http://hdl.handle.net/2133/18277
Aporte de:
Repositorio Hipermedial de la Universidad Nacional de Rosario (UNR) de Universidad Nacional de Rosario
id I15-R121-2133-18277
record_format dspace
institution Universidad Nacional de Rosario
institution_str I-15
repository_str R-121
collection Repositorio Hipermedial de la Universidad Nacional de Rosario (UNR)
language Inglés
orig_language_str_mv eng
topic Allylic azides
Equilibrium
Regioisomer predominance
spellingShingle Allylic azides
Equilibrium
Regioisomer predominance
Vallejos, Margarita M.
Labadie, Guillermo Roberto
Insight into the factors controlling the equilibrium of allylic azides
topic_facet Allylic azides
Equilibrium
Regioisomer predominance
description Several allylic azides with different double bond substitutions were studied to understand the factors, governing their equilibrium using density functional theory along with the quantum theory of atoms in molecules, non-covalent interactions and natural bond orbital approaches. The results showed that the hydroxyl group or heteroatoms in allylic azides interact with the molecule through an electrostatic weak interaction in each pair of regioisomers. The equilibrium shifts of substituted allylic azides, compared to non-substituted allylic azides, were not attributed to the presence of specific interactions, such as hydrogen bonds. The observed equilibrium shifts stemmed mainly from the strengthening and weakening of negative hyperconjugative interactions, which were affected by the weak interaction involving the proximal substituent in each regioisomer. A good linear correlation was obtained between the hyperconjugative energies of πC[double bond, length as m-dash]C→σ*Zb interactions and the calculated percentages of the secondary azide and tertiary azide in the equilibrium mixture. Also, the effect of the aromatic ring substituent was analysed using such approaches. This study not only provides insights into the factors controlling the stabilities of the substituted allylic azides, but also settles the basis to predict the regioisomer predominance in the equilibrium mixture.
format article
artículo
publishedVersion
author Vallejos, Margarita M.
Labadie, Guillermo Roberto
author_facet Vallejos, Margarita M.
Labadie, Guillermo Roberto
author_sort Vallejos, Margarita M.
title Insight into the factors controlling the equilibrium of allylic azides
title_short Insight into the factors controlling the equilibrium of allylic azides
title_full Insight into the factors controlling the equilibrium of allylic azides
title_fullStr Insight into the factors controlling the equilibrium of allylic azides
title_full_unstemmed Insight into the factors controlling the equilibrium of allylic azides
title_sort insight into the factors controlling the equilibrium of allylic azides
publisher Royal Society of Chemistry
publishDate 2020
url http://hdl.handle.net/2133/18277
http://hdl.handle.net/2133/18277
work_keys_str_mv AT vallejosmargaritam insightintothefactorscontrollingtheequilibriumofallylicazides
AT labadieguillermoroberto insightintothefactorscontrollingtheequilibriumofallylicazides
bdutipo_str Repositorios
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