Synthetic Zwitterionic Streptococcus pneumoniae Type 1 Oligosaccharides Carrying Labile O-Acetyl Esters

We herein report the first total synthesis of the Streptococcus pneumoniae serotype 1 (Sp1) oligosaccharide, a unique zwitterionic capsular polysaccharide carrying labile O-acetyl esters. The target oligosaccharides, featuring rare α-2,4-diamino-2,4,6-trideoxy galactose (AAT) and α-galacturonic acid...

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Autores: Wang, Zhen, Gimeno, Ana, Gutiérrez Lete, Marta, Overkleeft, Herman S., Van der Marel, Gijsbert A., Chiodo, Fabrizio, Jiménez Barbero, Jesús, Codee, Jeroen D. C.
Tipo de documento: artigo
Data de publicação:2023
País:España
Recursos:Universidad del País Vasco
Repositório:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/60282
Acesso em linha:http://hdl.handle.net/10810/60282
Access Level:Acceso aberto
Palavra-chave:acyl migration
bacterial oligosaccharides
glycosylation
helical structure
stereoselectivity
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spelling Synthetic Zwitterionic Streptococcus pneumoniae Type 1 Oligosaccharides Carrying Labile O-Acetyl EstersWang, ZhenGimeno, AnaGutiérrez Lete, MartaOverkleeft, Herman S.Van der Marel, Gijsbert A.Chiodo, FabrizioJiménez Barbero, JesúsCodee, Jeroen D. C.acyl migrationbacterial oligosaccharidesglycosylationhelical structurestereoselectivityWe herein report the first total synthesis of the Streptococcus pneumoniae serotype 1 (Sp1) oligosaccharide, a unique zwitterionic capsular polysaccharide carrying labile O-acetyl esters. The target oligosaccharides, featuring rare α-2,4-diamino-2,4,6-trideoxy galactose (AAT) and α-galacturonic acids, were assembled up to the 9-mer level, in a highly stereoselective manner using trisaccharide building blocks. The lability of the O-acetyl esters imposed a careful deprotection scheme to prevent migration and hydrolysis. The migration was investigated in detail at various pD values using NMR spectroscopy, to show that migration and hydrolysis of the C-3-O-acetyl esters readily takes place under neutral conditions. Structural investigation showed the oligomers to adopt a right-handed helical structure with the acetyl esters exposed on the periphery of the helix in close proximity of the neighboring AAT residues, thereby imposing conformational restrictions on the AATα1-4GalA(3OAc) glycosidic linkages, supporting the helical shape of the polysaccharide, that has been proposed to be critical for its unique biological activity.This work was supported by the Chinese Scholarship Council (CSC grant to Z. Wang), the Netherlands Organisation for Scientific Research (NWO VICI VI.C.182.020 to J.D.C.C), the European Research Council (ERC-2017-AdG, project number 788143-RE-CGLYCA NMR to J.J.B.) and Agencia Estatal de Investigación (Spain), projects RTI2018-094751-B-C21 and CIBERES, an initiative of Instituto de Salud Carlos III (ISCIII), Madrid, Spain.WileyEuropean Commission202320232023info:eu-repo/semantics/articleapplication/pdfhttp://hdl.handle.net/10810/60282reponame:Addi. Archivo Digital para la Docencia y la Investigacióninstname:Universidad del País VascoInglésinfo:eu-repo/grantAgreement/EC/ERC/788143info:eu-repo/grantAgreement/MICIU/RTI2018-094751-B-C21/https://onlinelibrary.wiley.com/doi/10.1002/anie.202211940info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by/3.0/es/© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.Atribución 3.0 Españaoai:addi.ehu.eus:10810/602822026-06-18T09:23:17Z
dc.title.none.fl_str_mv Synthetic Zwitterionic Streptococcus pneumoniae Type 1 Oligosaccharides Carrying Labile O-Acetyl Esters
title Synthetic Zwitterionic Streptococcus pneumoniae Type 1 Oligosaccharides Carrying Labile O-Acetyl Esters
spellingShingle Synthetic Zwitterionic Streptococcus pneumoniae Type 1 Oligosaccharides Carrying Labile O-Acetyl Esters
Wang, Zhen
acyl migration
bacterial oligosaccharides
glycosylation
helical structure
stereoselectivity
title_short Synthetic Zwitterionic Streptococcus pneumoniae Type 1 Oligosaccharides Carrying Labile O-Acetyl Esters
title_full Synthetic Zwitterionic Streptococcus pneumoniae Type 1 Oligosaccharides Carrying Labile O-Acetyl Esters
title_fullStr Synthetic Zwitterionic Streptococcus pneumoniae Type 1 Oligosaccharides Carrying Labile O-Acetyl Esters
title_full_unstemmed Synthetic Zwitterionic Streptococcus pneumoniae Type 1 Oligosaccharides Carrying Labile O-Acetyl Esters
title_sort Synthetic Zwitterionic Streptococcus pneumoniae Type 1 Oligosaccharides Carrying Labile O-Acetyl Esters
dc.creator.none.fl_str_mv Wang, Zhen
Gimeno, Ana
Gutiérrez Lete, Marta
Overkleeft, Herman S.
Van der Marel, Gijsbert A.
Chiodo, Fabrizio
Jiménez Barbero, Jesús
Codee, Jeroen D. C.
author Wang, Zhen
author_facet Wang, Zhen
Gimeno, Ana
Gutiérrez Lete, Marta
Overkleeft, Herman S.
Van der Marel, Gijsbert A.
Chiodo, Fabrizio
Jiménez Barbero, Jesús
Codee, Jeroen D. C.
author_role author
author2 Gimeno, Ana
Gutiérrez Lete, Marta
Overkleeft, Herman S.
Van der Marel, Gijsbert A.
Chiodo, Fabrizio
Jiménez Barbero, Jesús
Codee, Jeroen D. C.
author2_role author
author
author
author
author
author
author
dc.contributor.none.fl_str_mv European Commission
dc.subject.none.fl_str_mv acyl migration
bacterial oligosaccharides
glycosylation
helical structure
stereoselectivity
topic acyl migration
bacterial oligosaccharides
glycosylation
helical structure
stereoselectivity
description We herein report the first total synthesis of the Streptococcus pneumoniae serotype 1 (Sp1) oligosaccharide, a unique zwitterionic capsular polysaccharide carrying labile O-acetyl esters. The target oligosaccharides, featuring rare α-2,4-diamino-2,4,6-trideoxy galactose (AAT) and α-galacturonic acids, were assembled up to the 9-mer level, in a highly stereoselective manner using trisaccharide building blocks. The lability of the O-acetyl esters imposed a careful deprotection scheme to prevent migration and hydrolysis. The migration was investigated in detail at various pD values using NMR spectroscopy, to show that migration and hydrolysis of the C-3-O-acetyl esters readily takes place under neutral conditions. Structural investigation showed the oligomers to adopt a right-handed helical structure with the acetyl esters exposed on the periphery of the helix in close proximity of the neighboring AAT residues, thereby imposing conformational restrictions on the AATα1-4GalA(3OAc) glycosidic linkages, supporting the helical shape of the polysaccharide, that has been proposed to be critical for its unique biological activity.
publishDate 2023
dc.date.none.fl_str_mv 2023
2023
2023
dc.type.none.fl_str_mv info:eu-repo/semantics/article
format article
dc.identifier.none.fl_str_mv http://hdl.handle.net/10810/60282
url http://hdl.handle.net/10810/60282
dc.language.none.fl_str_mv Inglés
language_invalid_str_mv Inglés
dc.relation.none.fl_str_mv info:eu-repo/grantAgreement/EC/ERC/788143
info:eu-repo/grantAgreement/MICIU/RTI2018-094751-B-C21/
https://onlinelibrary.wiley.com/doi/10.1002/anie.202211940
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by/3.0/es/
Atribución 3.0 España
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by/3.0/es/
Atribución 3.0 España
dc.format.none.fl_str_mv application/pdf
dc.publisher.none.fl_str_mv Wiley
publisher.none.fl_str_mv Wiley
dc.source.none.fl_str_mv reponame:Addi. Archivo Digital para la Docencia y la Investigación
instname:Universidad del País Vasco
instname_str Universidad del País Vasco
reponame_str Addi. Archivo Digital para la Docencia y la Investigación
collection Addi. Archivo Digital para la Docencia y la Investigación
repository.name.fl_str_mv
repository.mail.fl_str_mv
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score 15,300719

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