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Synthesis of the Core Oligosaccharides of Lipooligosaccharides from Campylobacter jejuni : A Putative Cause of Guillain–Barré Syndrome
Author(s) -
Yoshida Fumi,
Yoshinaka Hiroki,
Tanaka Hidenori,
Hanashima Shinya,
Yamaguchi Yoshiki,
Ishihara Mikio,
Saburomaru Miyuki,
Kato Yuki,
Saito Risa,
Ando Hiromune,
Kiso Makoto,
Imamura Akihiro,
Ishida Hideharu
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201804862
Subject(s) - campylobacter jejuni , monosaccharide , glycan , ganglioside , glycosidic bond , stereochemistry , campylobacter , biochemistry , chemistry , mannose , glycosylation , biology , bacteria , glycoprotein , genetics , enzyme
Abstract The chemical synthesis of the highly branched core oligosaccharides of lipooligosaccharides (LOSs) found in Campylobacter jejuni , which causes Guillain–Barré syndrome by a preceding infection, is described. The target LOS mimics, consisting of eight or nine monosaccharides, were classified into three groups as key building blocks: ganglioside‐core tetra‐/pentasaccharides (GM1‐/GD1a‐like), l ‐ glycero ‐ d ‐ manno ‐heptose‐containing trisaccharides, and 3‐deoxy‐ d ‐ manno ‐2‐octulosonic acid (KDO) residues. These synthetic fragments were obtained from commercially available monosaccharides. Less obtainable l ‐ glycero ‐ d ‐ manno ‐heptose and KDO residues, as key components of the LOSs, were synthesized from p ‐methoxyphenyl d ‐mannoside and di‐ O ‐isopropylidene‐protected d ‐mannose, respectively. The synthesis of α‐KDO glycoside, as one of the most difficult stereocontrolled glycosidic constructions, was achieved by treating a 2,3‐ene derivative of KDO with phenylselenyl trifluoromethanesulfonate as a suitable α‐directing reagent. All synthetic blocks were constructed through a convergent synthetic route, which resulted in the first synthesis of structurally challenging LOS core glycans containing ganglioside GM1 and GD1a‐core sequences.