A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors
Four isomeric N-dimethylmaleoyl 4,6-O-benzylidene-protected d-hexosamine acceptors (2, 3, 4, and 5) with all possible configurations at C-1 and C-3 (e.g., derived from d-glucosamine and d-allosamine) were prepared, and the assessment of their O-3 relative reactivity through competition experiments u...
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2011
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00086215_v346_n5_p569_Colombo http://hdl.handle.net/20.500.12110/paper_00086215_v346_n5_p569_Colombo |
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paper:paper_00086215_v346_n5_p569_Colombo2023-06-08T14:33:00Z A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors Stortz, Carlos Arturo Competitive glycosylations Galactopyranosyl donor Glucosamine/allosamine acceptors Molecular modeling N-Dimethylmaleoyl group Benzylidene Comparative studies Electronic effects Galactopyranosyl donor Glucosamine/allosamine acceptors Glycosylations Hydroxyl groups N-Dimethylmaleoyl group NMR spectrum Relative reactivities Steric effect Experiments Glucosamine Hydrogen Molecular modeling Nuclear magnetic resonance spectroscopy Hydrogen bonds benzylidene derivative dimethylmaleoyl 4,6 o benzylidene glucosamine hexosamine hydroxyl group ozone trichloroacetimidic acid unclassified drug article chemical structure comparative study hydrogen bond isomer nuclear magnetic resonance spectroscopy priority journal synthesis temperature Glucosamine Glycosides Hydrogen Bonding Isomerism Magnetic Resonance Spectroscopy Molecular Structure Four isomeric N-dimethylmaleoyl 4,6-O-benzylidene-protected d-hexosamine acceptors (2, 3, 4, and 5) with all possible configurations at C-1 and C-3 (e.g., derived from d-glucosamine and d-allosamine) were prepared, and the assessment of their O-3 relative reactivity through competition experiments using the known per-O-acetylated d-galactopyranosyl trichloroacetimidate donor (15) was then carried out. The reactivities are in the order 4 ≫ 2 > 5 > 3. The analysis of the NMR spectra of 2-5 at different temperature and modeling experiments carried out on analogs of 2-5 (DFT) and on the acceptors themselves (MM) are coincident, and have helped to establish the stability of the different hydrogen bonds, and of the conformers which carry them. The whole results suggest that the electronic effects (hydrogen bonds) are required to explain the observed trend, in spite of the axial conformation of the most reactive hydroxyl group. The steric effects appear only when hydrogen bonds are weak. © 2011 Elsevier Ltd. All rights reserved. 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_00086215_v346_n5_p569_Colombo http://hdl.handle.net/20.500.12110/paper_00086215_v346_n5_p569_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 |
Competitive glycosylations Galactopyranosyl donor Glucosamine/allosamine acceptors Molecular modeling N-Dimethylmaleoyl group Benzylidene Comparative studies Electronic effects Galactopyranosyl donor Glucosamine/allosamine acceptors Glycosylations Hydroxyl groups N-Dimethylmaleoyl group NMR spectrum Relative reactivities Steric effect Experiments Glucosamine Hydrogen Molecular modeling Nuclear magnetic resonance spectroscopy Hydrogen bonds benzylidene derivative dimethylmaleoyl 4,6 o benzylidene glucosamine hexosamine hydroxyl group ozone trichloroacetimidic acid unclassified drug article chemical structure comparative study hydrogen bond isomer nuclear magnetic resonance spectroscopy priority journal synthesis temperature Glucosamine Glycosides Hydrogen Bonding Isomerism Magnetic Resonance Spectroscopy Molecular Structure |
| spellingShingle |
Competitive glycosylations Galactopyranosyl donor Glucosamine/allosamine acceptors Molecular modeling N-Dimethylmaleoyl group Benzylidene Comparative studies Electronic effects Galactopyranosyl donor Glucosamine/allosamine acceptors Glycosylations Hydroxyl groups N-Dimethylmaleoyl group NMR spectrum Relative reactivities Steric effect Experiments Glucosamine Hydrogen Molecular modeling Nuclear magnetic resonance spectroscopy Hydrogen bonds benzylidene derivative dimethylmaleoyl 4,6 o benzylidene glucosamine hexosamine hydroxyl group ozone trichloroacetimidic acid unclassified drug article chemical structure comparative study hydrogen bond isomer nuclear magnetic resonance spectroscopy priority journal synthesis temperature Glucosamine Glycosides Hydrogen Bonding Isomerism Magnetic Resonance Spectroscopy Molecular Structure Stortz, Carlos Arturo A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors |
| topic_facet |
Competitive glycosylations Galactopyranosyl donor Glucosamine/allosamine acceptors Molecular modeling N-Dimethylmaleoyl group Benzylidene Comparative studies Electronic effects Galactopyranosyl donor Glucosamine/allosamine acceptors Glycosylations Hydroxyl groups N-Dimethylmaleoyl group NMR spectrum Relative reactivities Steric effect Experiments Glucosamine Hydrogen Molecular modeling Nuclear magnetic resonance spectroscopy Hydrogen bonds benzylidene derivative dimethylmaleoyl 4,6 o benzylidene glucosamine hexosamine hydroxyl group ozone trichloroacetimidic acid unclassified drug article chemical structure comparative study hydrogen bond isomer nuclear magnetic resonance spectroscopy priority journal synthesis temperature Glucosamine Glycosides Hydrogen Bonding Isomerism Magnetic Resonance Spectroscopy Molecular Structure |
| description |
Four isomeric N-dimethylmaleoyl 4,6-O-benzylidene-protected d-hexosamine acceptors (2, 3, 4, and 5) with all possible configurations at C-1 and C-3 (e.g., derived from d-glucosamine and d-allosamine) were prepared, and the assessment of their O-3 relative reactivity through competition experiments using the known per-O-acetylated d-galactopyranosyl trichloroacetimidate donor (15) was then carried out. The reactivities are in the order 4 ≫ 2 > 5 > 3. The analysis of the NMR spectra of 2-5 at different temperature and modeling experiments carried out on analogs of 2-5 (DFT) and on the acceptors themselves (MM) are coincident, and have helped to establish the stability of the different hydrogen bonds, and of the conformers which carry them. The whole results suggest that the electronic effects (hydrogen bonds) are required to explain the observed trend, in spite of the axial conformation of the most reactive hydroxyl group. The steric effects appear only when hydrogen bonds are weak. © 2011 Elsevier Ltd. All rights reserved. |
| author |
Stortz, Carlos Arturo |
| author_facet |
Stortz, Carlos Arturo |
| author_sort |
Stortz, Carlos Arturo |
| title |
A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors |
| title_short |
A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors |
| title_full |
A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors |
| title_fullStr |
A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors |
| title_full_unstemmed |
A comparative study of the O-3 reactivity of isomeric N-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors |
| title_sort |
comparative study of the o-3 reactivity of isomeric n-dimethylmaleoyl- protected d-glucosamine and d-allosamine acceptors |
| publishDate |
2011 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00086215_v346_n5_p569_Colombo http://hdl.handle.net/20.500.12110/paper_00086215_v346_n5_p569_Colombo |
| work_keys_str_mv |
AT stortzcarlosarturo acomparativestudyoftheo3reactivityofisomericndimethylmaleoylprotecteddglucosamineanddallosamineacceptors AT stortzcarlosarturo comparativestudyoftheo3reactivityofisomericndimethylmaleoylprotecteddglucosamineanddallosamineacceptors |
| _version_ |
1768546141534683136 |