Synthesis of mono- and di-α-l-fucosylated 2-acetamido-2-deoxy-N-glycyl-β-d-glucopyranosylamines modeling N-glycoprotein carbohydrate-peptide bond region based on 2-acetamido-N-(N-tert-butyloxycarbonylglycyl)-2-deoxy-β-d-glucopyranosylamine

• Published in: Russian chemical bulletin Vol. 64; no. 6; pp. 1445 - 1450
• Main Authors: Likhosherstov, L. M., Novikova, O. S., Malysheva, N. N., Piskarev, V. E.
• Format: Journal Article
• Language: English
• Published: New York Springer US 01-06-2015
• Subjects: Chemistry; Chemistry and Materials Science; Chemistry/Food Science; Full Articles; Inorganic Chemistry; Organic Chemistry; fucose; carbohydrate-peptide bond; α; glucose; oligosaccharides; glycoproteins; 2-acetamido-2-desoxy; glycyl-β-glucopyranosylamines
• ISSN: 1066-5285; 1573-9171
• DOI: 10.1007/s11172-015-1030-3

A synthesis of glycyl-spacered
N
-β-glycosides of diand trisaccharides such as α-
l
-Fuc
p
-(1→3)-β-
d
-GlcNAc
p
-NHCOCH
2
NH
2
(
1
), α-
l
-Fuc
p
-(1→6)-[α-{asl}-Fuc
p
-(1→3)]-β-
d
-GlcNAc
p
-NHCOCH
2
NH
2
(
2
), α-
l
-Fuc
p
-(1→6)-β-
d
-GlcNAc
p
-NHCOCH
2
NH
2
({sn3}), which model the carbohydrate-peptide bond region of fucosylated
N
-glycoproteins of animals and plants, was accomplished. The synthesis was carried out by the fucosylation of unprotected
N
-glycoside β-{}scd-GlcNAc
p
-NHCOCH
2
NHBoc (Boc is the
tert
-butyloxycarbonyl) (
4
), 4,6-
O
-benzylidene derivative of compound
4
, and protected disaccharide
1
(α-
l
-Fuc
p
Bn
3
-(1→3)-β-
d
-GlcNAc
p
-NHCOCH
2
NHBoc (Bn is the benzyl)) with ethyl 2,3,4-tri-
O
-benzyl-1-thio-β-
l
-fucoside (in the presence of CuBr
2
and an excess of Et
4
NBr). A possibility of the selective ?-fucosylation of
N
-glycoside
4
at the primary hydroxy group in the presence of secondary hydroxy groups (in 34% yield) was demonstrated. Amino spacered
N
-glycosides
1
–
3
were obtained after the removal of protecting groups.