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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Autores principales:	Colombo, M.I., Rúveda, E.A., Stortz, C.A.
Formato:	JOUR
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:	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	todo:paper_14770520_v9_n8_p3020_Colombo
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spelling	todo:paper_14770520_v9_n8_p3020_Colombo2023-10-03T16:19:08Z Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach Colombo, M.I. Rúveda, E.A. Stortz, C.A. 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. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar 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 Colombo, M.I. Rúveda, E.A. Stortz, C.A. 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.
format	JOUR
author	Colombo, M.I. Rúveda, E.A. Stortz, C.A.
author_facet	Colombo, M.I. Rúveda, E.A. Stortz, C.A.
author_sort	Colombo, M.I.
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
url	http://hdl.handle.net/20.500.12110/paper_14770520_v9_n8_p3020_Colombo
work_keys_str_mv	AT colombomi regioselectivityoftheglycosylationofndimethylmaleoylprotectedhexosamineacceptorsanexperimentalanddftapproach AT ruvedaea regioselectivityoftheglycosylationofndimethylmaleoylprotectedhexosamineacceptorsanexperimentalanddftapproach AT stortzca regioselectivityoftheglycosylationofndimethylmaleoylprotectedhexosamineacceptorsanexperimentalanddftapproach
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Regioselectivity of the glycosylation of N-dimethylmaleoyl-protected hexosamine acceptors. An experimental and DFT approach

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