Efficient workflow for structural elucidation applied to solidagenone derivative: combining the speed of ML-J-DP4 screening with the precision of DP4+

Vista sencilla de ítem
dc.citation.titleTetrahedron Chem
dc.citation.volume14
dc.contributor.orcidhttps://orcid.org/0000-0002-8069-2793
dc.contributor.orcidhttps://orcid.org/0000-0002-7931-0639
dc.contributor.orcidhttps://orcid.org/0000-0002-5255-4721
dc.contributor.orcidhttps://orcid.org/0000-0002-6809-4723
dc.contributor.orcidhttps://orcid.org/0000-0002-8151-0306
dc.creatorCortés, Iván
dc.creatorTibaldi Bollati, María Luz
dc.creatorNicotra, Viviana Estela
dc.creatorGarcía, Manuela E.
dc.creatorSarotti, Ariel Marcelo
dc.date.accessioned2025-04-08T14:15:29Z
dc.date.available2025-04-08T14:15:29Z
dc.date.issued2025-03-06
dc.description.abstractThe derivatization of solidagenone through ring expansion, using the "Complexity to Diversity" synthetic strategy to obtain polyketones, yielded two products upon reaction of an intermediate with in situ-generated ruthenium tetroxide. As might happen, the spectroscopic and spectrometric data were inconclusive for the structural determination of one of these products. To address the issue, a ML-J-DP4//DP4+ workflow was studied, which allowed simultaneous determination of connectivity and relative configuration with high accuracy, while saving computational resources. Furthermore, during the calculation of NMR data at the DP4+ level, abnormally large errors were observed for the beta carbon of a polyhydroxylated conjugated enone. A literature analysis revealed that this behavior could be generalized, and after careful examination, it was determined to be the result of small geometric distortions caused by an overestimated network of intramolecular hydrogen bonds. To mitigate this common source of discrepancy, a heuristic solution was introduced as a proof of concept by in silico blocking of hydroxyl groups.
dc.description.filFil: Cortés, Iván. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química de Rosario (IQUIR-CONICET); Argentina.
dc.description.filFil: Tibaldi Bollati, María Luz. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto Multidisciplinario de Biología Vegetal (IMBIV-CONICET); Argentina.
dc.description.filFil: Nicotra, Viviana Estela. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto Multidisciplinario de Biología Vegetal (IMBIV-CONICET); Argentina.
dc.description.filFil: García, Manuela E. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto Multidisciplinario de Biología Vegetal (IMBIV-CONICET); Argentina.
dc.description.filFil: Sarotti, Ariel Marcelo. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas. Instituto de Química de Rosario (IQUIR-CONICET); Argentina.
dc.description.sponsorshipAgencia Nacional de Promoción de la Investigación, el Desarrollo Tecnológico y la Innovación (Agencia I+D+i): PICT-2019-4052, PICT-2021-CAT-II-00033, PICT-2020-SERIEA-02162
dc.description.sponsorshipConsejo Nacional de Investigaciones Científicas y Técnicas (CONICET): PIP 11220200102205CO, PIP 11220200101065CO
dc.description.sponsorshipOffice of Naval Research Global (ONR Global): grant N62909-21-1-2052
dc.description.sponsorshipSecretaría de Ciencia y Tecnología de la Universidad Nacional de Córdoba (SeCyT-UNC): 2023-CONSOLIDAR-33620230100785CB01
dc.description.versionpeerreviewed
dc.format.extent1-7
dc.identifier.e-issn2666-951X
dc.identifier.urihttps://hdl.handle.net/2133/29226
dc.language.isoen
dc.publisherElsevier
dc.relation.publisherversionhttps://doi.org/10.1016/j.tchem.2025.100125
dc.relation.publisherversionhttps://www.sciencedirect.com/science/article/pii/S2666951X25000075?via%3Dihub
dc.rightsopenAccess
dc.rights.holderCortés, Iván
dc.rights.holderTibaldi Bollati, María Luz
dc.rights.holderNicotra, Viviana Estela
dc.rights.holderGarcía, Manuela E.
dc.rights.holderSarotti, Ariel Marcelo
dc.rights.textAttribution-NonCommercial-NoDerivatives 4.0 Internationalen
dc.rights.urihttp://creativecommons.org/licenses/by-nc-nd/4.0/
dc.subjectSolidagenone derivatives
dc.subjectDFT-Calculations
dc.subjectNMR shifts
dc.subjectML-J-DP4
dc.subjectDP4+
dc.titleEfficient workflow for structural elucidation applied to solidagenone derivative: combining the speed of ML-J-DP4 screening with the precision of DP4+
dc.typearticulo
dc.type.collectionarticulo
dc.type.versionpublishedVersion

Archivos

Bloque original
Mostrando 1 - 1 de 1
Miniatura
Nombre:
File - 1-s2.0-S2666951X25000075-main.pdf
Tamaño:
2.46 MB
Formato:
Adobe Portable Document Format
Descargar
Bloque de licencias
Mostrando 1 - 1 de 1
Nombre:
license.txt
Tamaño:
3.87 KB
Formato:
Item-specific license agreed upon to submission
Descripción:
Descargar

Colecciones

(FBIOyF) Departamento de Química Orgánica - Artículos