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
- Institución
- Consejo Nacional de Investigaciones Científicas y Técnicas
- OAI Identificador
- oai:ri.conicet.gov.ar:11336/50399
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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 Técnicas2025-09-29T09:38:34Zoai: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:34982025-09-29 09:38:34.892CONICET 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 |
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CONICET Digital (CONICET) |
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CONICET Digital (CONICET) |
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Consejo Nacional de Investigaciones Científicas y Técnicas |
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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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1844613219260301312 |
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13.070432 |