Enzymatic Oligosaccharide Synthesis

F. Ouame and A. Guibert, Fmcto-oligosaccharides Enzymatic synthesis from sucrose, Zuckerind, 120 (1995) 793-798. 

S. Kojima, T. Hasegawa, T. Yonemura, K. Sasaki, K. Yamamoto, Y. Makimura, T. Takahashi, T. Suzuki, Y. Susuki, and K. Kobayashi, Ruthenium complexes carrying a disialo complex-type oligosaccharide Enzymatic synthesis and its application to a luminescent probe to detect influenza viruses, Chem. Commun. (2003) 1250-1251. 

Ouame F, Guibert A (1995) Fructo-oligosaccharides enzymatic synthesis from sucrose. Zuckerindustrie 120 793-798... 

Enzymatic Synthesis of Oligosaccharides Enzymatic Synthesis of Polysaccharides Enzymatic Synthesis of Glycoproteins Enzymatic Synthesis of Glycolipids Glycosylation of Natural Products... 

Nishio, T., Hakamata, W., Ogawa, M. et al. (2005) Investigations of a useful a-glycosidase for the enzymatic synthesis of rare sugar oligosaccharides. Journal of Applied Glycoscience, 52, 153-160. 

Murata, T. and Usui, T. (2006) Enzymatic synthesis of oligosaccharides and neoglycoconjugates. Bioscience, Biotechnology, and Biochemistry, 70, 1049-1059. 

Rabbani, S., Schwardt, O. and Ernst, B. (2006) Glycosyltransferases an efficient tool for the enzymatic synthesis of oligosaccharides and derivatives as well as mimetics thereof. Chimia, 60, 23-27. 

Fig. 8. Different products with sucrose analogues as substrates.115 Enzymatic synthesis of 1-kestose, 1-nystose, and their analogues by /(-fructofuranosidase of A. niger. Structures of fructo-oligosaccharides (A) commercial products, (B) mannose- (C) galactose-, and (D) xylose-substituted analogues.

T. Murata and T. Usui, Enzymatic synthesis of oligosaccharides and neoglyco-conjugates, Biosci. Biotechnol. Biochem., 70 (2006) 1049-1059. 

To catalyze a protective step in a chemo-enzymatic synthesis of sugar derivatives or of more complex oligosaccharides. 

In other reports, the lipase-catalyzed acylation of benzylidene derivatives of sugars, useful intermediates in the synthesis of oligosaccharides, has been described [42]. For example, the esterification of 4,6-O-benzylidene-a-D-glucopy-ranoside (13) with vinyl acetate by action of Pseudomonas cepacia lipase gave quantitatively the 2-O-acetate 13a. [42b] As a third case, it deserves to be mentioned the extensive work of Russo and coworkers for the chemo-enzymatic synthesis of milk oligosaccharides [43]. 

Enzymatic Synthesis of Sialic Acid, KDO, and Related Deoxyulosonic Acids, and of Oligosaccharides... 

The enzymatic synthesis of a hybrid type oligosaccharide on the hen ovalbumin with 13C-enriched galactose allowed the measurement of the 13C-NMR spectra of the whole glycoprotein and additionally, the determination of the correlation times of the protein and the oligosaccharide to 25 ns and 40-80 ns, respectively [168]. This implies that the carbohydrate, at least in its terminal monosaccharide constituents, has a much higher flexibility than the protein, and its flexibility is only little impeded by the attachment to the protein. 

On the other hand, the enzymatic synthesis of glycoconjugates and oligosaccharides leads to high product yields in a short time by stereo- and regioselective one-step reactions. All enzymatic reactions are easy to scale up and are carried out in aqueous media under mild conditions. A whole set of enzymes is now available to build up OAT bonds in monosaccharides, COP bonds in activated monosaccharides e.g. phosphorylated sugars or nucleotide sugars, and C-O-C bonds in di- and oligosaccharides (Fig. 1). However, all these enzymatic reactions are limited by the substrate spectrum of the individual enzyme. 

The ability of the hyperthermophilic glycosynthases to promote the synthesis of oligosaccharides is a clear example of how the unique characteristics of stability to high temperatures and acidic pH of the glycosidases from hyperthermophilic archaea allows the development of a novel strategy for the chemo-enzymatic synthesis of oligosaccharides. 

Moracci, M., Trincone, A., Cobucci-Ponzano, B., Perugino, G., Ciaramella, M., and Rossi, M. (2001) Enzymatic synthesis of oligosaccharides by two glycosyl hydrolases of Sulfolobus solfataricus. Extremophiles. 5 145-152. 

Schuster M, Wang P, Paulson JC, Wong CH, Solid-phase chemical-enzymatic synthesis of glycopeptides and oligosaccharides, J. Am. Chem. Soc., 116 1135-6, 1994. 

Chen, X., Kowal P., and Wang, P.G. Large-scale enzymatic synthesis of oligosaccharides, Curr. Op. Drug Disc. Devel., 3 756-763 (2000). 

Enzymatic synthesis of sugar esters and oligosaccharides from renewable resources, in Eiocatalysis in the Pharmaceutical and Biotechnological Industries (ed. R. Patel), CRC Press, pp. 465 90. 

Potato phosphorylase has successfully been employed for the enzymatic synthesis of 2-deoxyglucosyl 1-phosphate 135 (Scheme 45) [252]. D-glucal 136 was transferred onto maltotetrose 137 in the presence of the phosphorylase and catalytic amounts of phosphate to afford a modified maltooligosaccharide 138 that contained 2-deoxy-D-arabino-hexopyranosyl residues [253]. Formation of 2-deoxyglucosyl phosphate 135 can be explained by reverse phosphorolysis of the oligosaccharide 138. When soluble starch was employed as primer and an equimolar amount of phosphate was added, 2-deoxyglucosyl phosphate 135 was obtained in 50% isolated yield on a preparative scale. 

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