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Structure-Reactivit...
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Angles d'Ortoli, ThibaultStockholms universitet,Institutionen för organisk kemi
(författare)
Structure-Reactivity Relationships of Conformationally Armed Disaccharide Donors and Their Use in the Synthesis of a Hexasaccharide Related to the Capsular Polysaccharide from Streptococcus pneumoniae Type 37
- Artikel/kapitelEngelska2017
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2017-07-19
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American Chemical Society (ACS),2017
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electronicrdacarrier
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LIBRIS-ID:oai:DiVA.org:su-147106
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https://urn.kb.se/resolve?urn=urn:nbn:se:su:diva-147106URI
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https://doi.org/10.1021/acs.joc.7b01264DOI
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Språk:engelska
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Sammanfattning på:engelska
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Ämneskategori:ref swepub-contenttype
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Ämneskategori:art swepub-publicationtype
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Open Access 2019-09-01
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To advance the field of glycobiology, efficient synthesis methods of oligosaccharides and glycoconjugates are a requisite. In glycosylation reactions using superarmed donors, both selectivity and reactivity issues must be considered, and we herein investigate these aspects for differently protected beta-linked 2-O-glycosylated glucosyl donors carrying bulky tert-butyldimethylsilyl groups to different extents. The acceptors in reactions being secondary alcohols presents a challenging situation with respect to steric crowding. Conformational pyranose ring equilibria of the superarmed disaccharide donors with axial-rich substituents contained skew and boat conformations, and three-state models were generally assumed. With NIS/TfOH as the promotor, 2,6-di-tert-butyl-4-methylpyridine as the base, and a dichloromethane/toluene solvent mixture, ethyl 1-thio-beta-d-glucosyl disaccharide donors having 6-O-benzyl group(s) besides tert-butyldimethylsilyl groups were efficiently coupled at -40 degrees C to the hydroxyl group at position 3 of glucopyranosyl acceptors to form beta-(1 -> 2),beta-(1 -> 3)-linked trisaccharides, isolated in excellent 95% yield. The more axial-rich donors in skew and boat conformations are thus preorganized closer to the assumed transition state in these glycosylation reactions. The developed methodology was subsequently applied in the synthesis of a multibranched hexasaccharide related to the capsular polysaccharide from Streptococcus pneumoniae type 37, which consists of a beta-(1 -> 3)-linked backbone and a beta-(1 -> 2)-linked side chain of D-glucosyl residues in disaccharide repeating units.
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Hamark, ChristofferStockholms universitet,Institutionen för organisk kemi(Swepub:su)chha8123
(författare)
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Widmalm, GöranStockholms universitet,Institutionen för organisk kemi(Swepub:su)gw
(författare)
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Stockholms universitetInstitutionen för organisk kemi
(creator_code:org_t)
Sammanhörande titlar
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Ingår i:Journal of Organic Chemistry: American Chemical Society (ACS)82:15, s. 8123-81400022-32631520-6904
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