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Furanosyl Oxocarbenium Ion Conformational Energy Landscape Maps as a Tool to Study the Glycosylation Stereoselectivity of 2‐Azidofuranoses, 2‐Fluorofuranoses and Methyl Furanosyl Uronates

The 3D shape of glycosyl oxocarbenium ions determines their stability and reactivity and the stereochemical course of S(N)1 reactions taking place on these reactive intermediates is dictated by the conformation of these species. The nature and configuration of functional groups on the carbohydrate r...

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Autores principales: van der Vorm, Stefan, Hansen, Thomas, van Rijssel, Erwin R., Dekkers, Rolf, Madern, Jerre M., Overkleeft, Herman S., Filippov, Dmitri V., van der Marel, Gijsbert A., Codée, Jeroen D. C.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: John Wiley and Sons Inc. 2019
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6563709/
https://www.ncbi.nlm.nih.gov/pubmed/30882938
http://dx.doi.org/10.1002/chem.201900651
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author van der Vorm, Stefan
Hansen, Thomas
van Rijssel, Erwin R.
Dekkers, Rolf
Madern, Jerre M.
Overkleeft, Herman S.
Filippov, Dmitri V.
van der Marel, Gijsbert A.
Codée, Jeroen D. C.
author_facet van der Vorm, Stefan
Hansen, Thomas
van Rijssel, Erwin R.
Dekkers, Rolf
Madern, Jerre M.
Overkleeft, Herman S.
Filippov, Dmitri V.
van der Marel, Gijsbert A.
Codée, Jeroen D. C.
author_sort van der Vorm, Stefan
collection PubMed
description The 3D shape of glycosyl oxocarbenium ions determines their stability and reactivity and the stereochemical course of S(N)1 reactions taking place on these reactive intermediates is dictated by the conformation of these species. The nature and configuration of functional groups on the carbohydrate ring affect the stability of glycosyl oxocarbenium ions and control the overall shape of the cations. We herein map the stereoelectronic substituent effects of the C2‐azide, C2‐fluoride and C4‐carboxylic acid ester on the stability and reactivity of the complete suite of diastereoisomeric furanoses by using a combined computational and experimental approach. Surprisingly, all furanosyl donors studied react in a highly stereoselective manner to provide the 1,2‐cis products, except for the reactions in the xylose series. The 1,2‐cis selectivity for the ribo‐, arabino‐ and lyxo‐configured furanosides can be traced back to the lowest‐energy (3) E or E (3) conformers of the intermediate oxocarbenium ions. The lack of selectivity for the xylosyl donors is related to the occurrence of oxocarbenium ions adopting other conformations.
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spelling pubmed-65637092019-06-20 Furanosyl Oxocarbenium Ion Conformational Energy Landscape Maps as a Tool to Study the Glycosylation Stereoselectivity of 2‐Azidofuranoses, 2‐Fluorofuranoses and Methyl Furanosyl Uronates van der Vorm, Stefan Hansen, Thomas van Rijssel, Erwin R. Dekkers, Rolf Madern, Jerre M. Overkleeft, Herman S. Filippov, Dmitri V. van der Marel, Gijsbert A. Codée, Jeroen D. C. Chemistry Full Papers The 3D shape of glycosyl oxocarbenium ions determines their stability and reactivity and the stereochemical course of S(N)1 reactions taking place on these reactive intermediates is dictated by the conformation of these species. The nature and configuration of functional groups on the carbohydrate ring affect the stability of glycosyl oxocarbenium ions and control the overall shape of the cations. We herein map the stereoelectronic substituent effects of the C2‐azide, C2‐fluoride and C4‐carboxylic acid ester on the stability and reactivity of the complete suite of diastereoisomeric furanoses by using a combined computational and experimental approach. Surprisingly, all furanosyl donors studied react in a highly stereoselective manner to provide the 1,2‐cis products, except for the reactions in the xylose series. The 1,2‐cis selectivity for the ribo‐, arabino‐ and lyxo‐configured furanosides can be traced back to the lowest‐energy (3) E or E (3) conformers of the intermediate oxocarbenium ions. The lack of selectivity for the xylosyl donors is related to the occurrence of oxocarbenium ions adopting other conformations. John Wiley and Sons Inc. 2019-04-17 2019-05-23 /pmc/articles/PMC6563709/ /pubmed/30882938 http://dx.doi.org/10.1002/chem.201900651 Text en © 2019 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by-nc-nd/4.0/ License, which permits use and distribution in any medium, provided the original work is properly cited, the use is non‐commercial and no modifications or adaptations are made.
spellingShingle Full Papers
van der Vorm, Stefan
Hansen, Thomas
van Rijssel, Erwin R.
Dekkers, Rolf
Madern, Jerre M.
Overkleeft, Herman S.
Filippov, Dmitri V.
van der Marel, Gijsbert A.
Codée, Jeroen D. C.
Furanosyl Oxocarbenium Ion Conformational Energy Landscape Maps as a Tool to Study the Glycosylation Stereoselectivity of 2‐Azidofuranoses, 2‐Fluorofuranoses and Methyl Furanosyl Uronates
title Furanosyl Oxocarbenium Ion Conformational Energy Landscape Maps as a Tool to Study the Glycosylation Stereoselectivity of 2‐Azidofuranoses, 2‐Fluorofuranoses and Methyl Furanosyl Uronates
title_full Furanosyl Oxocarbenium Ion Conformational Energy Landscape Maps as a Tool to Study the Glycosylation Stereoselectivity of 2‐Azidofuranoses, 2‐Fluorofuranoses and Methyl Furanosyl Uronates
title_fullStr Furanosyl Oxocarbenium Ion Conformational Energy Landscape Maps as a Tool to Study the Glycosylation Stereoselectivity of 2‐Azidofuranoses, 2‐Fluorofuranoses and Methyl Furanosyl Uronates
title_full_unstemmed Furanosyl Oxocarbenium Ion Conformational Energy Landscape Maps as a Tool to Study the Glycosylation Stereoselectivity of 2‐Azidofuranoses, 2‐Fluorofuranoses and Methyl Furanosyl Uronates
title_short Furanosyl Oxocarbenium Ion Conformational Energy Landscape Maps as a Tool to Study the Glycosylation Stereoselectivity of 2‐Azidofuranoses, 2‐Fluorofuranoses and Methyl Furanosyl Uronates
title_sort furanosyl oxocarbenium ion conformational energy landscape maps as a tool to study the glycosylation stereoselectivity of 2‐azidofuranoses, 2‐fluorofuranoses and methyl furanosyl uronates
topic Full Papers
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6563709/
https://www.ncbi.nlm.nih.gov/pubmed/30882938
http://dx.doi.org/10.1002/chem.201900651
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