Structural analysis of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-D-allopyranoside by X-ray crystallography, NMR, and QM calculations: Hydrogen bonding and comparison of dens...

Autores
Colombo, María Inés; Ruveda, Edmundo; Gorlova, Olga; Lalancette, Roger; Stortz, Carlos Arturo
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The crystal structure of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-d-allopyranoside was solved in order to gain insight into the hydrogen bond features which can be determining features in the glycosylation regioselectivity observed for this compound. An intramolecular hydrogen bond between the hydroxyl H(O)3 and a carbonyl oxygen from the dimethylmaleoyl (DMM) group was observed. This was in agreement with previous NMR temperature shift determinations and molecular modeling. The determination has also found an intermolecular hydrogen bond between the second hydroxyl H(O)4 and the other carbonyl oxygen (generated by symmetry) from DMM. The crystal structure was optimized by five different functionals, namely the hybrid methods B3LYP, M06-2X, B3PW91, and PBE0, and the pure functional PBE, and the optimized geometries were compared with the crystal geometry and with MM3. An excellent coincidence of the geometries was found with the five quantum methods, with minor details deviating from this coincidence. PBE tends to yield larger bond distances, whereas M06-2X fails slightly to match the exocyclic torsion angles for the sugar moiety. In any case, the differences are small, implying that any of these functionals can accurately emulate the geometries of a complex carbohydrate derivative like this one.
Fil: Colombo, María Inés. 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: Ruveda, Edmundo. 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: Gorlova, Olga. Rutgers University; Estados Unidos
Fil: Lalancette, Roger. Rutgers University; Estados Unidos
Fil: Stortz, Carlos Arturo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina
Materia
Allosamine
Conformation
Crystal Structure
Density Functional Theory
N-Dimethylmaleloyl Group
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/68276
Acceder
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network_name_str CONICET Digital (CONICET)
spelling Structural analysis of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-D-allopyranoside by X-ray crystallography, NMR, and QM calculations: Hydrogen bonding and comparison of density functionalsColombo, María InésRuveda, EdmundoGorlova, OlgaLalancette, RogerStortz, Carlos ArturoAllosamineConformationCrystal StructureDensity Functional TheoryN-Dimethylmaleloyl Grouphttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The crystal structure of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-d-allopyranoside was solved in order to gain insight into the hydrogen bond features which can be determining features in the glycosylation regioselectivity observed for this compound. An intramolecular hydrogen bond between the hydroxyl H(O)3 and a carbonyl oxygen from the dimethylmaleoyl (DMM) group was observed. This was in agreement with previous NMR temperature shift determinations and molecular modeling. The determination has also found an intermolecular hydrogen bond between the second hydroxyl H(O)4 and the other carbonyl oxygen (generated by symmetry) from DMM. The crystal structure was optimized by five different functionals, namely the hybrid methods B3LYP, M06-2X, B3PW91, and PBE0, and the pure functional PBE, and the optimized geometries were compared with the crystal geometry and with MM3. An excellent coincidence of the geometries was found with the five quantum methods, with minor details deviating from this coincidence. PBE tends to yield larger bond distances, whereas M06-2X fails slightly to match the exocyclic torsion angles for the sugar moiety. In any case, the differences are small, implying that any of these functionals can accurately emulate the geometries of a complex carbohydrate derivative like this one.Fil: Colombo, María Inés. 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: Ruveda, Edmundo. 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: Gorlova, Olga. Rutgers University; Estados UnidosFil: Lalancette, Roger. Rutgers University; Estados UnidosFil: Stortz, Carlos Arturo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; ArgentinaElsevier2012-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/68276Colombo, María Inés; Ruveda, Edmundo; Gorlova, Olga; Lalancette, Roger; Stortz, Carlos Arturo; Structural analysis of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-D-allopyranoside by X-ray crystallography, NMR, and QM calculations: Hydrogen bonding and comparison of density functionals; Elsevier; Carbohydrate Research; 353; 5-2012; 79-850008-6215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.carres.2012.03.025info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0008621512001334info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-nd/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T12:08:58Zoai:ri.conicet.gov.ar:11336/68276instacron: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 12:08:59.036CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Structural analysis of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-D-allopyranoside by X-ray crystallography, NMR, and QM calculations: Hydrogen bonding and comparison of density functionals
title Structural analysis of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-D-allopyranoside by X-ray crystallography, NMR, and QM calculations: Hydrogen bonding and comparison of density functionals
spellingShingle Structural analysis of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-D-allopyranoside by X-ray crystallography, NMR, and QM calculations: Hydrogen bonding and comparison of density functionals
Colombo, María Inés
Allosamine
Conformation
Crystal Structure
Density Functional Theory
N-Dimethylmaleloyl Group
title_short Structural analysis of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-D-allopyranoside by X-ray crystallography, NMR, and QM calculations: Hydrogen bonding and comparison of density functionals
title_full Structural analysis of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-D-allopyranoside by X-ray crystallography, NMR, and QM calculations: Hydrogen bonding and comparison of density functionals
title_fullStr Structural analysis of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-D-allopyranoside by X-ray crystallography, NMR, and QM calculations: Hydrogen bonding and comparison of density functionals
title_full_unstemmed Structural analysis of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-D-allopyranoside by X-ray crystallography, NMR, and QM calculations: Hydrogen bonding and comparison of density functionals
title_sort Structural analysis of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-D-allopyranoside by X-ray crystallography, NMR, and QM calculations: Hydrogen bonding and comparison of density functionals
dc.creator.none.fl_str_mv Colombo, María Inés
Ruveda, Edmundo
Gorlova, Olga
Lalancette, Roger
Stortz, Carlos Arturo
author Colombo, María Inés
author_facet Colombo, María Inés
Ruveda, Edmundo
Gorlova, Olga
Lalancette, Roger
Stortz, Carlos Arturo
author_role author
author2 Ruveda, Edmundo
Gorlova, Olga
Lalancette, Roger
Stortz, Carlos Arturo
author2_role author
author
author
author
dc.subject.none.fl_str_mv Allosamine
Conformation
Crystal Structure
Density Functional Theory
N-Dimethylmaleloyl Group
topic Allosamine
Conformation
Crystal Structure
Density Functional Theory
N-Dimethylmaleloyl Group
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 crystal structure of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-d-allopyranoside was solved in order to gain insight into the hydrogen bond features which can be determining features in the glycosylation regioselectivity observed for this compound. An intramolecular hydrogen bond between the hydroxyl H(O)3 and a carbonyl oxygen from the dimethylmaleoyl (DMM) group was observed. This was in agreement with previous NMR temperature shift determinations and molecular modeling. The determination has also found an intermolecular hydrogen bond between the second hydroxyl H(O)4 and the other carbonyl oxygen (generated by symmetry) from DMM. The crystal structure was optimized by five different functionals, namely the hybrid methods B3LYP, M06-2X, B3PW91, and PBE0, and the pure functional PBE, and the optimized geometries were compared with the crystal geometry and with MM3. An excellent coincidence of the geometries was found with the five quantum methods, with minor details deviating from this coincidence. PBE tends to yield larger bond distances, whereas M06-2X fails slightly to match the exocyclic torsion angles for the sugar moiety. In any case, the differences are small, implying that any of these functionals can accurately emulate the geometries of a complex carbohydrate derivative like this one.
Fil: Colombo, María Inés. 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: Ruveda, Edmundo. 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: Gorlova, Olga. Rutgers University; Estados Unidos
Fil: Lalancette, Roger. Rutgers University; Estados Unidos
Fil: Stortz, Carlos Arturo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Centro de Investigaciones en Hidratos de Carbono. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Centro de Investigaciones en Hidratos de Carbono; Argentina
description The crystal structure of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-d-allopyranoside was solved in order to gain insight into the hydrogen bond features which can be determining features in the glycosylation regioselectivity observed for this compound. An intramolecular hydrogen bond between the hydroxyl H(O)3 and a carbonyl oxygen from the dimethylmaleoyl (DMM) group was observed. This was in agreement with previous NMR temperature shift determinations and molecular modeling. The determination has also found an intermolecular hydrogen bond between the second hydroxyl H(O)4 and the other carbonyl oxygen (generated by symmetry) from DMM. The crystal structure was optimized by five different functionals, namely the hybrid methods B3LYP, M06-2X, B3PW91, and PBE0, and the pure functional PBE, and the optimized geometries were compared with the crystal geometry and with MM3. An excellent coincidence of the geometries was found with the five quantum methods, with minor details deviating from this coincidence. PBE tends to yield larger bond distances, whereas M06-2X fails slightly to match the exocyclic torsion angles for the sugar moiety. In any case, the differences are small, implying that any of these functionals can accurately emulate the geometries of a complex carbohydrate derivative like this one.
publishDate 2012
dc.date.none.fl_str_mv 2012-05
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/11336/68276
Colombo, María Inés; Ruveda, Edmundo; Gorlova, Olga; Lalancette, Roger; Stortz, Carlos Arturo; Structural analysis of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-D-allopyranoside by X-ray crystallography, NMR, and QM calculations: Hydrogen bonding and comparison of density functionals; Elsevier; Carbohydrate Research; 353; 5-2012; 79-85
0008-6215
CONICET Digital
CONICET
url http://hdl.handle.net/11336/68276
identifier_str_mv Colombo, María Inés; Ruveda, Edmundo; Gorlova, Olga; Lalancette, Roger; Stortz, Carlos Arturo; Structural analysis of methyl 6-O-benzyl-2-deoxy-2-dimethylmaleimido- α-D-allopyranoside by X-ray crystallography, NMR, and QM calculations: Hydrogen bonding and comparison of density functionals; Elsevier; Carbohydrate Research; 353; 5-2012; 79-85
0008-6215
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.carres.2012.03.025
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0008621512001334
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-nd/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv Elsevier
publisher.none.fl_str_mv Elsevier
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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