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Synthesis of 6‐Sulfonatomethyl Thioglycosides by Nucleophilic Substitution: Methods to Prevent 1→6 Anomeric Group Migration of Thioglycoside 6‐ O ‐Triflates
Author(s) -
Herczeg Mihály,
Mező Erika,
Eszenyi Dániel,
Lázár László,
Csávás Magdolna,
Bereczki Ilona,
Antus Sándor,
Borbás Anikó
Publication year - 2013
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201300681
Subject(s) - chemistry , anomer , sulfonium , trifluoromethanesulfonate , nucleophile , moiety , stereochemistry , nucleophilic substitution , uronic acid , bicyclic molecule , selectivity , medicinal chemistry , organic chemistry , polysaccharide , salt (chemistry) , catalysis
of a sulfonatomethyl moiety into the primary position of thioglycosides by nucleophilic displacement of the corresponding 6‐ O ‐triflate is described. The 1→6 migration of the anomeric group, which inevitably occurs through a bicyclic sulfonium ion intermediate, from conformationally flexible β‐thioglycosides was prevented by using an α‐thioglycoside or conformationally locked β‐thioglycoside as the starting material. The thioglycoside 6‐sulfonic acids showed excellent α‐selectivity during synthesis of uronic acid containing heparinoid trisaccharides.