On the effect of intramolecular H-bonding in the configurational assessment of polyhydroxylated compounds with computational methods : The hyacinthacines case
| Autor: | Ariel M. Sarotti, Maximiliano Sortino, María Marta Zanardi |
|---|---|
| Jazyk: | angličtina |
| Rok vydání: | 2019 |
| Předmět: |
Hydroxylation
010402 general chemistry 01 natural sciences Biochemistry Analytical Chemistry chemistry.chemical_compound Computational chemistry Carbohydrate Conformation ISOMEROS METODO COMPUTACIONAL Pyrrolizidine Alkaloids PYRROLIZIDINES 010405 organic chemistry Hydrogen bond Organic Chemistry Ciencias Químicas Hydrogen Bonding Stereoisomerism QUIMICA General Medicine HYACINTHACINES H-BONDING 0104 chemical sciences Química Orgánica Models Chemical chemistry Intramolecular force Pyrrolizidine Quantum Theory Thermodynamics Artifacts DP4+ CIENCIAS NATURALES Y EXACTAS |
| Zdroj: | Carbohydrate Research. Vol. 474, 2019 Repositorio Institucional (UCA) Pontificia Universidad Católica Argentina instacron:UCA |
| Popis: | 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%). Fil: Zanardi, Maria Marta. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina. Pontificia Universidad Católica Argentina "Santa María de los Buenos Aires". Facultad de Química e Ingeniería del Rosario; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; Argentina Fil: Sortino, Maximiliano Andrés. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario; Argentina. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina Fil: Sarotti, Ariel Marcelo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Rosario. Instituto de Química Rosario. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química Rosario; Argentina |
| Databáze: | OpenAIRE |
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