Determination of the relative configuration of terminal and spiroepoxides by computational methods : advantages of the inclusion of unscaled data
- Autores
- Zanardi, María Marta; Suárez, Alejandra G.; Sarotti, Ariel Marcelo
- Año de publicación
- 2017
- Idioma
- inglés
- Tipo de recurso
- artículo
- Estado
- versión publicada
- Descripción
- Fil: Zanardi, María Marta. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina
Fil: Zanardi, María Marta. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas de Argentina; Argentina
Fil: Suárez, Alejandra G. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina
Fil: Sarotti, Ariel Marcelo. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmaceútias; Argentina
Fil: Zanardi, María Marta. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario; Argentina
Fil: Suárez, Alejandra G. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas de Argentina; Argentina
Fil: Sarotti, Ariel Marcelo. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas de Argentina; Argentina
Abstract: The assignment of the relative configuration of spiroepoxides or related quaternary carbon-containing oxiranes can be troublesome and difficult to achieve. The use of GIAO NMR shift calculations can provide helpful assistance in challenging cases of structural elucidation. In this regard, the DP4 probability is one of the most popular methods to be employed when only one set of experimental data is available, though modest results were obtained when dealing with spiroepoxides. Recently, we introduced an improved probability (DP4+) that includes the use of both scaled and unscaled NMR data computed at higher levels of theory. Here, we report a comprehensive study to explore the scope and limitations of the DP4+ methodology in the stereoassignment of terminal or spiroepoxides bearing a wide variety of molecular complexity and conformational freedom. The excellent levels of correct classification achieved were interpreted on the basis of a constructive compensation of errors upon using both scaled and unscaled proton and carbon data. The advantages of the DP4+ methodology in solving two case studies that could not be unequivocally assigned by NOE experiments are also provided. - Fuente
- The Journal of Organic Chemistry Vol. 82, 2017
- Materia
-
QUIMICA
QUIMICA ORGANICA
COMPUTACION - Nivel de accesibilidad
- acceso abierto
- Condiciones de uso
- https://creativecommons.org/licenses/by-nc-sa/4.0/
- Repositorio
- Institución
- Pontificia Universidad Católica Argentina
- OAI Identificador
- oai:ucacris:123456789/5649
Ver los metadatos del registro completo
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Determination of the relative configuration of terminal and spiroepoxides by computational methods : advantages of the inclusion of unscaled dataZanardi, María MartaSuárez, Alejandra G.Sarotti, Ariel MarceloQUIMICAQUIMICA ORGANICACOMPUTACIONFil: Zanardi, María Marta. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; ArgentinaFil: Zanardi, María Marta. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas de Argentina; ArgentinaFil: Suárez, Alejandra G. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; ArgentinaFil: Sarotti, Ariel Marcelo. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmaceútias; ArgentinaFil: Zanardi, María Marta. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario; ArgentinaFil: Suárez, Alejandra G. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas de Argentina; ArgentinaFil: Sarotti, Ariel Marcelo. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas de Argentina; ArgentinaAbstract: The assignment of the relative configuration of spiroepoxides or related quaternary carbon-containing oxiranes can be troublesome and difficult to achieve. The use of GIAO NMR shift calculations can provide helpful assistance in challenging cases of structural elucidation. In this regard, the DP4 probability is one of the most popular methods to be employed when only one set of experimental data is available, though modest results were obtained when dealing with spiroepoxides. Recently, we introduced an improved probability (DP4+) that includes the use of both scaled and unscaled NMR data computed at higher levels of theory. Here, we report a comprehensive study to explore the scope and limitations of the DP4+ methodology in the stereoassignment of terminal or spiroepoxides bearing a wide variety of molecular complexity and conformational freedom. The excellent levels of correct classification achieved were interpreted on the basis of a constructive compensation of errors upon using both scaled and unscaled proton and carbon data. The advantages of the DP4+ methodology in solving two case studies that could not be unequivocally assigned by NOE experiments are also provided.ACS Publications2017info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfhttps://repositorio.uca.edu.ar/handle/123456789/56491520-6904 (online)10.1021/acs.joc.6b02129Zanardi, M.M., Suárez, A.G., Sarotti, A.M. Determination of the relative configuration of terminal and spiroepoxides by computational methods : advantages of the inclusion of unscaled data [en línea]. The Journal of Organic Chemistry. 2017 (82). Disponible en: https://repositorio.uca.edu.ar/handle/123456789/5649The Journal of Organic Chemistry Vol. 82, 2017reponame:Repositorio Institucional (UCA)instname:Pontificia Universidad Católica Argentinaenginfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/4.0/2025-07-03T10:56:09Zoai:ucacris:123456789/5649instacron:UCAInstitucionalhttps://repositorio.uca.edu.ar/Universidad privadaNo correspondehttps://repositorio.uca.edu.ar/oaiclaudia_fernandez@uca.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:25852025-07-03 10:56:09.835Repositorio Institucional (UCA) - Pontificia Universidad Católica Argentinafalse |
dc.title.none.fl_str_mv |
Determination of the relative configuration of terminal and spiroepoxides by computational methods : advantages of the inclusion of unscaled data |
title |
Determination of the relative configuration of terminal and spiroepoxides by computational methods : advantages of the inclusion of unscaled data |
spellingShingle |
Determination of the relative configuration of terminal and spiroepoxides by computational methods : advantages of the inclusion of unscaled data Zanardi, María Marta QUIMICA QUIMICA ORGANICA COMPUTACION |
title_short |
Determination of the relative configuration of terminal and spiroepoxides by computational methods : advantages of the inclusion of unscaled data |
title_full |
Determination of the relative configuration of terminal and spiroepoxides by computational methods : advantages of the inclusion of unscaled data |
title_fullStr |
Determination of the relative configuration of terminal and spiroepoxides by computational methods : advantages of the inclusion of unscaled data |
title_full_unstemmed |
Determination of the relative configuration of terminal and spiroepoxides by computational methods : advantages of the inclusion of unscaled data |
title_sort |
Determination of the relative configuration of terminal and spiroepoxides by computational methods : advantages of the inclusion of unscaled data |
dc.creator.none.fl_str_mv |
Zanardi, María Marta Suárez, Alejandra G. Sarotti, Ariel Marcelo |
author |
Zanardi, María Marta |
author_facet |
Zanardi, María Marta Suárez, Alejandra G. Sarotti, Ariel Marcelo |
author_role |
author |
author2 |
Suárez, Alejandra G. Sarotti, Ariel Marcelo |
author2_role |
author author |
dc.subject.none.fl_str_mv |
QUIMICA QUIMICA ORGANICA COMPUTACION |
topic |
QUIMICA QUIMICA ORGANICA COMPUTACION |
dc.description.none.fl_txt_mv |
Fil: Zanardi, María Marta. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina Fil: Zanardi, María Marta. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas de Argentina; Argentina Fil: Suárez, Alejandra G. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina Fil: Sarotti, Ariel Marcelo. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmaceútias; Argentina Fil: Zanardi, María Marta. Pontificia Universidad Católica Argentina. Facultad de Química e Ingeniería del Rosario; Argentina Fil: Suárez, Alejandra G. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas de Argentina; Argentina Fil: Sarotti, Ariel Marcelo. Instituto de Química Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas de Argentina; Argentina Abstract: The assignment of the relative configuration of spiroepoxides or related quaternary carbon-containing oxiranes can be troublesome and difficult to achieve. The use of GIAO NMR shift calculations can provide helpful assistance in challenging cases of structural elucidation. In this regard, the DP4 probability is one of the most popular methods to be employed when only one set of experimental data is available, though modest results were obtained when dealing with spiroepoxides. Recently, we introduced an improved probability (DP4+) that includes the use of both scaled and unscaled NMR data computed at higher levels of theory. Here, we report a comprehensive study to explore the scope and limitations of the DP4+ methodology in the stereoassignment of terminal or spiroepoxides bearing a wide variety of molecular complexity and conformational freedom. The excellent levels of correct classification achieved were interpreted on the basis of a constructive compensation of errors upon using both scaled and unscaled proton and carbon data. The advantages of the DP4+ methodology in solving two case studies that could not be unequivocally assigned by NOE experiments are also provided. |
description |
Fil: Zanardi, María Marta. Universidad Nacional de Rosario. Facultad de Ciencias Bioquímicas y Farmacéuticas; Argentina |
publishDate |
2017 |
dc.date.none.fl_str_mv |
2017 |
dc.type.none.fl_str_mv |
info:eu-repo/semantics/article info:eu-repo/semantics/publishedVersion http://purl.org/coar/resource_type/c_6501 info:ar-repo/semantics/articulo |
format |
article |
status_str |
publishedVersion |
dc.identifier.none.fl_str_mv |
https://repositorio.uca.edu.ar/handle/123456789/5649 1520-6904 (online) 10.1021/acs.joc.6b02129 Zanardi, M.M., Suárez, A.G., Sarotti, A.M. Determination of the relative configuration of terminal and spiroepoxides by computational methods : advantages of the inclusion of unscaled data [en línea]. The Journal of Organic Chemistry. 2017 (82). Disponible en: https://repositorio.uca.edu.ar/handle/123456789/5649 |
url |
https://repositorio.uca.edu.ar/handle/123456789/5649 |
identifier_str_mv |
1520-6904 (online) 10.1021/acs.joc.6b02129 Zanardi, M.M., Suárez, A.G., Sarotti, A.M. Determination of the relative configuration of terminal and spiroepoxides by computational methods : advantages of the inclusion of unscaled data [en línea]. The Journal of Organic Chemistry. 2017 (82). Disponible en: https://repositorio.uca.edu.ar/handle/123456789/5649 |
dc.language.none.fl_str_mv |
eng |
language |
eng |
dc.rights.none.fl_str_mv |
info:eu-repo/semantics/openAccess https://creativecommons.org/licenses/by-nc-sa/4.0/ |
eu_rights_str_mv |
openAccess |
rights_invalid_str_mv |
https://creativecommons.org/licenses/by-nc-sa/4.0/ |
dc.format.none.fl_str_mv |
application/pdf |
dc.publisher.none.fl_str_mv |
ACS Publications |
publisher.none.fl_str_mv |
ACS Publications |
dc.source.none.fl_str_mv |
The Journal of Organic Chemistry Vol. 82, 2017 reponame:Repositorio Institucional (UCA) instname:Pontificia Universidad Católica Argentina |
reponame_str |
Repositorio Institucional (UCA) |
collection |
Repositorio Institucional (UCA) |
instname_str |
Pontificia Universidad Católica Argentina |
repository.name.fl_str_mv |
Repositorio Institucional (UCA) - Pontificia Universidad Católica Argentina |
repository.mail.fl_str_mv |
claudia_fernandez@uca.edu.ar |
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