Cargando…

An orthogonal and reactivity-based one-pot glycosylation strategy for both glycan and nucleoside synthesis: access to TMG-chitotriomycin, lipochitooligosaccharides and capuramycin

Both glycans (O-glycosides) and nucleosides (N-glycosides) play important roles in numerous biological processes. Chemical synthesis is a reliable and effective means to solve the attainability issues of these essential biomolecules. However, due to the stereo- and regiochemical issues during glycan...

Descripción completa

Detalles Bibliográficos
Autores principales: He, Haiqing, Xu, Lili, Sun, Roujing, Zhang, Yunqin, Huang, Yingying, Chen, Zixi, Li, Penghua, Yang, Rui, Xiao, Guozhi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: The Royal Society of Chemistry 2021
Materias:
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179548/
https://www.ncbi.nlm.nih.gov/pubmed/34163751
http://dx.doi.org/10.1039/d0sc06815b
_version_ 1783703806660313088
author He, Haiqing
Xu, Lili
Sun, Roujing
Zhang, Yunqin
Huang, Yingying
Chen, Zixi
Li, Penghua
Yang, Rui
Xiao, Guozhi
author_facet He, Haiqing
Xu, Lili
Sun, Roujing
Zhang, Yunqin
Huang, Yingying
Chen, Zixi
Li, Penghua
Yang, Rui
Xiao, Guozhi
author_sort He, Haiqing
collection PubMed
description Both glycans (O-glycosides) and nucleosides (N-glycosides) play important roles in numerous biological processes. Chemical synthesis is a reliable and effective means to solve the attainability issues of these essential biomolecules. However, due to the stereo- and regiochemical issues during glycan assembly, together with problems including the poor solubility and nucleophilicity of nucleobases in nucleoside synthesis, the development of one-pot glycosylation strategies toward efficient synthesis of both glycans and nucleosides remains poor and challenging. Here, we report the first orthogonal and reactivity-based one-pot glycosylation strategy suitable for both glycan and nucleoside synthesis on the basis of glycosyl ortho-(1-phenylvinyl)benzoates. This one-pot glycosylation strategy not only inherits the advantages including no aglycon transfers, no undesired interference of departing species, and no unpleasant odors associated with the previously developed orthogonal one-pot glycosylation strategy based on glycosyl ortho-alkynylbenzoates, but also highly expands the scope (glycans and nucleosides) and increases the number of leaving groups that could be employed for the multistep one-pot synthesis (up to the formation of four different glycosidic bonds). In particular, the current one-pot glycosylation strategy is successfully applied to the total synthesis of a promising tuberculosis drug lead capuramycin and the divergent and formal synthesis of TMG-chitotriomycin with potent and specific inhibition activities toward β-N-acetylglucosaminidases and important endosymbiotic lipochitooligosaccharides including the Nod factor and the Myc factor, which represents one of the most efficient and straightforward synthetic routes toward these biologically salient molecules.
format Online
Article
Text
id pubmed-8179548
institution National Center for Biotechnology Information
language English
publishDate 2021
publisher The Royal Society of Chemistry
record_format MEDLINE/PubMed
spelling pubmed-81795482021-06-22 An orthogonal and reactivity-based one-pot glycosylation strategy for both glycan and nucleoside synthesis: access to TMG-chitotriomycin, lipochitooligosaccharides and capuramycin He, Haiqing Xu, Lili Sun, Roujing Zhang, Yunqin Huang, Yingying Chen, Zixi Li, Penghua Yang, Rui Xiao, Guozhi Chem Sci Chemistry Both glycans (O-glycosides) and nucleosides (N-glycosides) play important roles in numerous biological processes. Chemical synthesis is a reliable and effective means to solve the attainability issues of these essential biomolecules. However, due to the stereo- and regiochemical issues during glycan assembly, together with problems including the poor solubility and nucleophilicity of nucleobases in nucleoside synthesis, the development of one-pot glycosylation strategies toward efficient synthesis of both glycans and nucleosides remains poor and challenging. Here, we report the first orthogonal and reactivity-based one-pot glycosylation strategy suitable for both glycan and nucleoside synthesis on the basis of glycosyl ortho-(1-phenylvinyl)benzoates. This one-pot glycosylation strategy not only inherits the advantages including no aglycon transfers, no undesired interference of departing species, and no unpleasant odors associated with the previously developed orthogonal one-pot glycosylation strategy based on glycosyl ortho-alkynylbenzoates, but also highly expands the scope (glycans and nucleosides) and increases the number of leaving groups that could be employed for the multistep one-pot synthesis (up to the formation of four different glycosidic bonds). In particular, the current one-pot glycosylation strategy is successfully applied to the total synthesis of a promising tuberculosis drug lead capuramycin and the divergent and formal synthesis of TMG-chitotriomycin with potent and specific inhibition activities toward β-N-acetylglucosaminidases and important endosymbiotic lipochitooligosaccharides including the Nod factor and the Myc factor, which represents one of the most efficient and straightforward synthetic routes toward these biologically salient molecules. The Royal Society of Chemistry 2021-02-23 /pmc/articles/PMC8179548/ /pubmed/34163751 http://dx.doi.org/10.1039/d0sc06815b Text en This journal is © The Royal Society of Chemistry https://creativecommons.org/licenses/by-nc/3.0/
spellingShingle Chemistry
He, Haiqing
Xu, Lili
Sun, Roujing
Zhang, Yunqin
Huang, Yingying
Chen, Zixi
Li, Penghua
Yang, Rui
Xiao, Guozhi
An orthogonal and reactivity-based one-pot glycosylation strategy for both glycan and nucleoside synthesis: access to TMG-chitotriomycin, lipochitooligosaccharides and capuramycin
title An orthogonal and reactivity-based one-pot glycosylation strategy for both glycan and nucleoside synthesis: access to TMG-chitotriomycin, lipochitooligosaccharides and capuramycin
title_full An orthogonal and reactivity-based one-pot glycosylation strategy for both glycan and nucleoside synthesis: access to TMG-chitotriomycin, lipochitooligosaccharides and capuramycin
title_fullStr An orthogonal and reactivity-based one-pot glycosylation strategy for both glycan and nucleoside synthesis: access to TMG-chitotriomycin, lipochitooligosaccharides and capuramycin
title_full_unstemmed An orthogonal and reactivity-based one-pot glycosylation strategy for both glycan and nucleoside synthesis: access to TMG-chitotriomycin, lipochitooligosaccharides and capuramycin
title_short An orthogonal and reactivity-based one-pot glycosylation strategy for both glycan and nucleoside synthesis: access to TMG-chitotriomycin, lipochitooligosaccharides and capuramycin
title_sort orthogonal and reactivity-based one-pot glycosylation strategy for both glycan and nucleoside synthesis: access to tmg-chitotriomycin, lipochitooligosaccharides and capuramycin
topic Chemistry
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8179548/
https://www.ncbi.nlm.nih.gov/pubmed/34163751
http://dx.doi.org/10.1039/d0sc06815b
work_keys_str_mv AT hehaiqing anorthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT xulili anorthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT sunroujing anorthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT zhangyunqin anorthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT huangyingying anorthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT chenzixi anorthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT lipenghua anorthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT yangrui anorthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT xiaoguozhi anorthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT hehaiqing orthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT xulili orthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT sunroujing orthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT zhangyunqin orthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT huangyingying orthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT chenzixi orthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT lipenghua orthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT yangrui orthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin
AT xiaoguozhi orthogonalandreactivitybasedonepotglycosylationstrategyforbothglycanandnucleosidesynthesisaccesstotmgchitotriomycinlipochitooligosaccharidesandcapuramycin