Synthesis of GDP-5-thiosugars and Their Use as Glycosyl Donor Substrates for Glycosyltransferases

Two thiopyranoside analogues of GDP-sugars, GDP-5-thio-d-mannose (14) and GDP-5-thio-l-fucose (15), were synthesized. The syntheses included the phosphorylations of tetra-O-acetyl-5-thio-d-mannosyl bromide (4) and tri-O-benzoyl-l-fucosyl bromide (6) with silver dibenzyl phosphate, deprotection of th...

Full description

Saved in:
Bibliographic Details
Published in:Journal of organic chemistry 2003-08, Vol.68 (16), p.6400-6406
Main Authors: Tsuruta, Osamu, Yuasa, Hideya, Hashimoto, Hironobu, Sujino, Keiko, Otter, Albin, Li, Hong, Palcic, Monica M
Format: Article
Language:English
Subjects:
Carbohydrate Sequence
Carbohydrates. Nucleosides and nucleotides
Chemistry
Chromatography, Thin Layer
Disaccharides - chemical synthesis
Electrophoresis, Capillary
Exact sciences and technology
Glycosylation
Glycosyltransferases - metabolism
Guanosine Diphosphate - analogs & derivatives
Guanosine Diphosphate - chemical synthesis
Guanosine Diphosphate - chemistry
Indicators and Reagents
Magnetic Resonance Spectroscopy
Models, Molecular
Molecular Conformation
Molecular Sequence Data
Nucleosides, nucleotides and oligonucleotides
Organic chemistry
Preparations and properties
Thioglycosides - chemical synthesis
Thioglycosides - chemistry
Trisaccharides - chemical synthesis
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:Two thiopyranoside analogues of GDP-sugars, GDP-5-thio-d-mannose (14) and GDP-5-thio-l-fucose (15), were synthesized. The syntheses included the phosphorylations of tetra-O-acetyl-5-thio-d-mannosyl bromide (4) and tri-O-benzoyl-l-fucosyl bromide (6) with silver dibenzyl phosphate, deprotection of the phosphate groups, and condensation of the deprotected phosphates with GMP-imidazolidate (13) in the presence of MgCl2. These GDP-sugar analogues were found to be donor substrates for α(1,2)mannosyltransferase and α(1,3)fucosyltransferase, affording a 5-thiomannose-containing disaccharide (18) and a 5-thiofucose-containing trisaccharide (21), respectively. The conformation of the disaccharide analogue 18 was similar to that of its native counterpart by ROESY. These findings for GDP-5-thiosugars together with previous demonstrations of enzymatic transfer from UDP-5-thiosugars will allow the production of panels of oligosaccharide analogues with hydrolase-resistant properties.
ISSN:0022-3263
1520-6904
DOI:10.1021/jo0300035