Determination of the Relative Configuration of Terminal and Spiroepoxides by Computational Methods: Advantages of the Inclusion of Unscaled Data

Autores
Zanardi, Maria Marta; Suarez, Alejandra Graciela; Sarotti, Ariel Marcelo
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
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.
Fil: Zanardi, Maria Marta. 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. Pontificia Universidad Católica Argentina ; Argentina
Fil: Suarez, Alejandra Graciela. 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
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
Materia
NMR
OXIRANES
LEVOGLUCOSENONE
COMPUTATIONAL STUDIES
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/50399
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Determination of the Relative Configuration of Terminal and Spiroepoxides by Computational Methods: Advantages of the Inclusion of Unscaled DataZanardi, Maria MartaSuarez, Alejandra GracielaSarotti, Ariel MarceloNMROXIRANESLEVOGLUCOSENONECOMPUTATIONAL STUDIEShttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The 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.Fil: Zanardi, Maria Marta. 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. Pontificia Universidad Católica Argentina ; ArgentinaFil: Suarez, Alejandra Graciela. 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; ArgentinaFil: 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; ArgentinaAmerican Chemical Society2017-02info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/50399Zanardi, Maria Marta; Suarez, Alejandra Graciela; Sarotti, Ariel Marcelo; Determination of the Relative Configuration of Terminal and Spiroepoxides by Computational Methods: Advantages of the Inclusion of Unscaled Data; American Chemical Society; Journal of Organic Chemistry; 82; 4; 2-2017; 1873-18790022-3263CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.6b02129info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.joc.6b02129info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:06:50Zoai:ri.conicet.gov.ar:11336/50399instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-10-22 11:06:50.8CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
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, Maria Marta
NMR
OXIRANES
LEVOGLUCOSENONE
COMPUTATIONAL STUDIES
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, Maria Marta
Suarez, Alejandra Graciela
Sarotti, Ariel Marcelo
author Zanardi, Maria Marta
author_facet Zanardi, Maria Marta
Suarez, Alejandra Graciela
Sarotti, Ariel Marcelo
author_role author
author2 Suarez, Alejandra Graciela
Sarotti, Ariel Marcelo
author2_role author
author
dc.subject.none.fl_str_mv NMR
OXIRANES
LEVOGLUCOSENONE
COMPUTATIONAL STUDIES
topic NMR
OXIRANES
LEVOGLUCOSENONE
COMPUTATIONAL STUDIES
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv 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.
Fil: Zanardi, Maria Marta. 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. Pontificia Universidad Católica Argentina ; Argentina
Fil: Suarez, Alejandra Graciela. 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
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
description 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.
publishDate 2017
dc.date.none.fl_str_mv 2017-02
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 http://hdl.handle.net/11336/50399
Zanardi, Maria Marta; Suarez, Alejandra Graciela; Sarotti, Ariel Marcelo; Determination of the Relative Configuration of Terminal and Spiroepoxides by Computational Methods: Advantages of the Inclusion of Unscaled Data; American Chemical Society; Journal of Organic Chemistry; 82; 4; 2-2017; 1873-1879
0022-3263
CONICET Digital
CONICET
url http://hdl.handle.net/11336/50399
identifier_str_mv Zanardi, Maria Marta; Suarez, Alejandra Graciela; Sarotti, Ariel Marcelo; Determination of the Relative Configuration of Terminal and Spiroepoxides by Computational Methods: Advantages of the Inclusion of Unscaled Data; American Chemical Society; Journal of Organic Chemistry; 82; 4; 2-2017; 1873-1879
0022-3263
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.joc.6b02129
info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/acs.joc.6b02129
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 12.982451

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