Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach

Both anomers of the methyl glycoside of 6-O-benzyl-N-dimethylmaleoyl-d- allosamine (6 and 7) are glycosylated exclusively on O3 when reacting with the trichloroacetimidate of peracetylated α-d-galactopyranose (5). This regioselectivity is expected for 6, the α-anomer, as a strong hydrogen bond of it...

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Autor principal:	Stortz, Carlos Arturo
Publicado:	2011
Materias:	Anomers Carbonyl groups Charged intermediates DFT study Galactopyranose Glycosylated Glycosylation reactions Methyl glycosides Related compounds Temperature dependence Esterification Glycosylation Hydrogen Reaction intermediates Regioselectivity Sugars Hydrogen bonds hexosamine article chemical structure chemistry Fourier analysis glycosylation methylation Fourier Analysis Hexosamines Methylation Models, Molecular Molecular Structure
Acceso en línea:	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14770520_v9_n8_p3020_Colombo http://hdl.handle.net/20.500.12110/paper_14770520_v9_n8_p3020_Colombo
Aporte de:	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires

id	paper:paper_14770520_v9_n8_p3020_Colombo
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spelling	paper:paper_14770520_v9_n8_p3020_Colombo2023-06-08T16:18:07Z Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach Stortz, Carlos Arturo Anomers Carbonyl groups Charged intermediates DFT study Galactopyranose Glycosylated Glycosylation reactions Methyl glycosides Related compounds Temperature dependence Esterification Glycosylation Hydrogen Reaction intermediates Regioselectivity Sugars Hydrogen bonds hexosamine article chemical structure chemistry Fourier analysis glycosylation methylation Fourier Analysis Glycosylation Hexosamines Methylation Models, Molecular Molecular Structure Both anomers of the methyl glycoside of 6-O-benzyl-N-dimethylmaleoyl-d- allosamine (6 and 7) are glycosylated exclusively on O3 when reacting with the trichloroacetimidate of peracetylated α-d-galactopyranose (5). This regioselectivity is expected for 6, the α-anomer, as a strong hydrogen bond of its H(O)3 with the carbonyl group of the dimethylmaleoyl group occurs, as shown by NMR temperature dependence. However, this hydrogen bond was not encountered experimentally for 7, the β-anomer. A DFT study of the energies implied in an analog of the glycosylation reaction charged intermediate has explained neatly this behavior, in terms of strong hydrogen bonds occurring at these charged intermediates. This approach explains both the experimental regioselectivities found for 6 and 7, but furthermore the calculations have shown a marked agreement with the regioselectivities found for other related compounds in the literature. © 2011 The Royal Society of Chemistry. Fil:Stortz, C.A. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; Argentina. 2011 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14770520_v9_n8_p3020_Colombo http://hdl.handle.net/20.500.12110/paper_14770520_v9_n8_p3020_Colombo
institution	Universidad de Buenos Aires
institution_str	I-28
repository_str	R-134
collection	Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
topic	Anomers Carbonyl groups Charged intermediates DFT study Galactopyranose Glycosylated Glycosylation reactions Methyl glycosides Related compounds Temperature dependence Esterification Glycosylation Hydrogen Reaction intermediates Regioselectivity Sugars Hydrogen bonds hexosamine article chemical structure chemistry Fourier analysis glycosylation methylation Fourier Analysis Glycosylation Hexosamines Methylation Models, Molecular Molecular Structure
spellingShingle	Anomers Carbonyl groups Charged intermediates DFT study Galactopyranose Glycosylated Glycosylation reactions Methyl glycosides Related compounds Temperature dependence Esterification Glycosylation Hydrogen Reaction intermediates Regioselectivity Sugars Hydrogen bonds hexosamine article chemical structure chemistry Fourier analysis glycosylation methylation Fourier Analysis Glycosylation Hexosamines Methylation Models, Molecular Molecular Structure Stortz, Carlos Arturo Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach
topic_facet	Anomers Carbonyl groups Charged intermediates DFT study Galactopyranose Glycosylated Glycosylation reactions Methyl glycosides Related compounds Temperature dependence Esterification Glycosylation Hydrogen Reaction intermediates Regioselectivity Sugars Hydrogen bonds hexosamine article chemical structure chemistry Fourier analysis glycosylation methylation Fourier Analysis Glycosylation Hexosamines Methylation Models, Molecular Molecular Structure
description	Both anomers of the methyl glycoside of 6-O-benzyl-N-dimethylmaleoyl-d- allosamine (6 and 7) are glycosylated exclusively on O3 when reacting with the trichloroacetimidate of peracetylated α-d-galactopyranose (5). This regioselectivity is expected for 6, the α-anomer, as a strong hydrogen bond of its H(O)3 with the carbonyl group of the dimethylmaleoyl group occurs, as shown by NMR temperature dependence. However, this hydrogen bond was not encountered experimentally for 7, the β-anomer. A DFT study of the energies implied in an analog of the glycosylation reaction charged intermediate has explained neatly this behavior, in terms of strong hydrogen bonds occurring at these charged intermediates. This approach explains both the experimental regioselectivities found for 6 and 7, but furthermore the calculations have shown a marked agreement with the regioselectivities found for other related compounds in the literature. © 2011 The Royal Society of Chemistry.
author	Stortz, Carlos Arturo
author_facet	Stortz, Carlos Arturo
author_sort	Stortz, Carlos Arturo
title	Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach
title_short	Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach
title_full	Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach
title_fullStr	Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach
title_full_unstemmed	Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach
title_sort	regioselectivity of the glycosylation of n-dimethylmaleoyl-protected hexosamine acceptors. an experimental and dft approach
publishDate	2011
url	https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14770520_v9_n8_p3020_Colombo http://hdl.handle.net/20.500.12110/paper_14770520_v9_n8_p3020_Colombo
work_keys_str_mv	AT stortzcarlosarturo regioselectivityoftheglycosylationofndimethylmaleoylprotectedhexosamineacceptorsanexperimentalanddftapproach
_version_	1768545432952111104

Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach

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