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Convergent Synthesis of a Bisecting N ‐Acetylglucosamine (GlcNAc)‐Containing N‐Glycan
Author(s) -
Manabe Yoshiyuki,
Shomura Hiroki,
Minamoto Naoya,
Nagasaki Masahiro,
Takakura Yohei,
Tanaka Katsunori,
Silipo Alba,
Molinaro Antonio,
Fukase Koichi
Publication year - 2018
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201800367
Subject(s) - glycan , chemistry , glycosylation , n acetylglucosamine , steric effects , oxocarbenium , tetrasaccharide , glycobiology , stereochemistry , glycosyl donor , convergent synthesis , combinatorial chemistry , organic chemistry , biochemistry , glycoprotein , catalysis , polysaccharide , nucleophile , enzyme
The chemical synthesis of a bisecting N ‐acetylglucosamine (GlcNAc)‐containing N‐glycan was achieved by a convergent synthetic route through [4+2] and [6+2] glycosylations. This synthetic route reduced the number of reaction steps, although the key glycosylations were challenging in terms of yields and selectivities owing to steric hindrance at the glycosylation site and a lack of neighboring group participation. The yields of these glycosylations were enhanced by stabilizing the oxocarbenium ion intermediate through ether coordination. Glycosyl donor protecting groups were explored in an effort to realize perfect α selectivity by manipulating remote participation. The simultaneous glycosylations of a tetrasaccharide with two disaccharides was investigated to efficiently construct a bisecting GlcNAc‐containing N‐glycan.