Synthesis of dTDP-6-Deoxy-4-ketoglucose and Analogues with Native and Recombinant dTDP-Glucose-4,6-dehydratase

✍ Scribed by Dipl.-Chem. Andreas Stein; Prof. Dr. Maria-Regina Kula; Dr. Lothar Elling; Dipl.-Biol. Stefan Verseck; Dr. Werner Klaffke

• Book ID: 101556146
• Publisher: John Wiley and Sons
• Year: 1995
• Tongue: English
• Weight: 271 KB
• Volume: 34
• Category: Article
• ISSN: 0044-8249
• DOI: 10.1002/anie.199517481

✦ Synopsis

Activated ketoglucose derivatives play a key role in the biosynthesis of deoxygenated oligo-and polysaccharides, because they represent the branching points in many biosynthetic pathways leading to 2.6-and 3.6-dideoxy-and -aminodeoxysugars, and branched deoxysugars. Although the gene clusters for the biosynthesis of deoxysugars in bacteria have been localized and the corresponding enzymes should now be available. the insufficient availability of the intermediates and the lack of effective analytical methods still hampers detailed investigations." -3 1 Solving these problems is necessary before the chemoenzymatic synthesis of deoxyoligosaccharides is as successful as that of N-glycosidically bound glycans.

In one of the activating pathways in bacteria leading to deoxyoligosaccharides, dTDP-i>-glucose 1 (dTDP = thymidine-5'-diphosphate) is converted into dTDP-L-rhamnose via the corresponding 6-deoxy-4-keto intermediate 2, which in turn is synthesized by dTDP-~-glucose-4,6-dehydratase [EC 421.461 (Scheme 1). This enzyme from different sources has been used for the synthesis of labeled substrates.[". 51 The recent enzymatic synthesis of dTDP-6-deoxy-4-ketogIucose 2 marks progress in this area.lbl During the preparation of this manuscript.