Synthesis and Use of Glycosyl Phosphates as Glycosyl Donors

Plante, Obadiah J.; Andrade, Rodrigo; Seeberger, Peter H.

doi:10.1021/ol9905452

Cited by 144 publications

(105 citation statements)

References 26 publications

(18 reference statements)

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“…[184] A number of other approaches have since emerged. [185] Like trichloroacetimidate donors, both aand b-glycosyl phosphates can be prepared readily, and they are stable enough to be stored for several months at 0 8C. The a isomers can be formed from the b isomers by acid-catalyzed anomerization.…”

Section: Glycosyl Phosphates and Phosphitesmentioning

confidence: 99%

New Principles for Glycoside‐Bond Formation

2009

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Increased understanding of the important roles that oligosaccharides and glycoconjugates play in biological processes has led to a demand for significant amounts of these materials for biological, medicinal, and pharmacological studies. Therefore, tremendous effort has been made to develop new procedures for the synthesis of glycosides, whereby the main focus is often the formation of the glycosidic bonds. Accordingly, quite a few review articles have been published over the past few years on glycoside synthesis; however, most are confined to either a specific type of glycoside or a specific strategy for glycoside synthesis. In this Review, new principles for the formation of glycoside bonds are discussed. Developments, mainly in the last ten years, that have led to significant advances in oligosaccharide and glycoconjugate synthesis have been compiled and are evaluated.

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Section: Glycosyl Phosphates and Phosphitesmentioning

confidence: 99%

New Principles for Glycoside‐Bond Formation

2009

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“…In these reactions, βGlc1P functions as an activated donor for the α-glucosylation of different monosaccharides. Like other glycosylphosphates, it can also be used as donor for chemical glycosylation reactions [4]. Furthermore, these compounds can have direct applications in antiinflammatory or immunosuppressive drugs [5] or can be used to manufacture agents with vitamin D-like activity for preventing or curing skin diseases, parathyroid diseases, malignant tumors and bone diseases [6].…”

Section: Introductionmentioning

confidence: 99%

Enzymatic production of β‐D‐glucose‐1‐phosphate from trehalose

Borght¹,

Desmet²,

Soetaert³

2010

Biotechnology Journal

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beta-D-Glucose-1-phosphate (beta Glc1P) is an efficient glucosyl donor for both enzymatic and chemical glycosylation reactions but is currently very costly and not available in large amounts. This article provides an efficient production method of beta Glc1P from trehalose and phosphate using the thermostable trehalose phosphorylase from Thermoanaerobacter brockii. At the process temperature of 60 C, Escherichia coli expression host cells are lysed and cell treatment prior to the reaction is, therefore, not required. In this way, the theoretical maximum yield of 26% could be easily achieved. Two different purification strategies have been compared, anion exchange chromatography or carbohydrate removal by treatment with trehalase and yeast, followed by chemical phosphate precipitation. In a next step, beta Glc1P was precipitated with ethanol but this did not induce crystallization, in contrast to what ist observed with other glycosylphosphates. After conversion of the product to its cyclohexylammonium salt, however, crystals could be readily obtained. Although both purification methods were quantitative (>99% recovery), a large amount of product (50%) was lost during crystallization. Nevertheless, a production process for crystalline beta Glc1P is now available from the cheap substrates trehalose and inorganic phosphate

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“…[21] For example, pure a-and b-anomeric isomers 1 a and 1 b were reacted with acceptor 2 (Table 1), in the presence of trimethylsilyl trifluoromethanesulfonate (TMSOTf) (1 equiv) in CH 2 Cl 2 , a-phosphate 1 a was completely activated at À78 8C within 5 min, while the b-phosphate 1 b was only partially activated over a short time. On the other hand, phosphate 1 b could be fully activated by TMSOTf at higher temperature (À50 8C) in only 5 min.…”

mentioning

confidence: 99%

“…The difference in reactivity between 1 a and 1 b is smaller when compared with the galactosyl phosphate donor. [21] Encouraged by these preliminary results, we investigated the glycosyl donor properties of 1 a in producing naturally occurring sialoside linkages (Table 2). Regioselective sialylation of galactopyranoside 4,6-diols 4 (Table 2, entry 2) under TMSOTf activation in CH 2 Cl 2 at À78 8C, gave sialylated (2!6)disaccharides 5 with complete a selectivity and high yields.…”

mentioning

confidence: 99%