On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case

Abstract: Hyacinthacines are important members of the pyrrolizidine family, with several compounds having ambiguous, revised or unverified structures. Herein we thoroughly explored the performance DP4 and DP4+ for the in silico stereoassignment of hyacinthacines A1, A2 and five synthetic isomers. Th...

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Detalles Bibliográficos
Autores principales: Zanardi, María Marta, Sortino, Maximiliano A., Sarotti, Ariel M.
Formato: Artículo
Lenguaje:Inglés
Publicado: Elsevier 2019
Materias:
ISOMEROS
METODO COMPUTACIONAL
QUIMICA
Acceso en línea:https://repositorio.uca.edu.ar/handle/123456789/9025
https://doi.org/10.1016/j.carres.2019.01.011
Aporte de:
Repositorio Institucional de la Universidad Católica Argentina (UCA) de Universidad Católica Argentina
id I33-R139123456789-9025
record_format dspace
institution Universidad Católica Argentina
institution_str I-33
repository_str R-139
collection Repositorio Institucional de la Universidad Católica Argentina (UCA)
language Inglés
topic ISOMEROS
METODO COMPUTACIONAL
QUIMICA
spellingShingle ISOMEROS
METODO COMPUTACIONAL
QUIMICA
Zanardi, María Marta
Sortino, Maximiliano A.
Sarotti, Ariel M.
On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case
topic_facet ISOMEROS
METODO COMPUTACIONAL
QUIMICA
description Abstract: Hyacinthacines are important members of the pyrrolizidine family, with several compounds having ambiguous, revised or unverified structures. Herein we thoroughly explored the performance DP4 and DP4+ for the in silico stereoassignment of hyacinthacines A1, A2 and five synthetic isomers. The results suggested that the quality of the predictions strongly depended on the conformational landscape provided by DFT energies, with five compounds correctly assigned. In the two cases incorrectly classified we found that the source of the problem was conformational in nature, with spurious conformations being considerably over-stabilized by intramolecular H-bondings. We showed that neglecting such shapes resulted in a noteworthy improvement, with all compounds correctly assigned in high confidence (>99.9%).
format Artículo
author Zanardi, María Marta
Sortino, Maximiliano A.
Sarotti, Ariel M.
author_facet Zanardi, María Marta
Sortino, Maximiliano A.
Sarotti, Ariel M.
author_sort Zanardi, María Marta
title On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case
title_short On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case
title_full On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case
title_fullStr On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case
title_full_unstemmed On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case
title_sort on the effect of intramolecular h-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : the hyacinthacines case
publisher Elsevier
publishDate 2019
url https://repositorio.uca.edu.ar/handle/123456789/9025
https://doi.org/10.1016/j.carres.2019.01.011
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