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
Repositorio Institucional (UCA)
Institución
Pontificia Universidad Católica Argentina
OAI Identificador
oai:ucacris:123456789/5649
Acceder
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oai_identifier_str oai:ucacris:123456789/5649
network_acronym_str RIUCA
repository_id_str 2585
network_name_str Repositorio Institucional (UCA)
spelling 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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score 12.982451

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