Synthesis of Hyaluronic Acid Oligomers Using Ph<sub>2</sub>SO/Tf<sub>2</sub>O-Mediated Glycosylations

Dinkelaar, Jasper; Codée, Jeroen D. C.; Bos, Leendert J. van den; Overkleeft, Herman S.; Marel, Gijsbert A. van der

doi:10.1021/jo070704s

Cited by 42 publications

(35 citation statements)

References 15 publications

(17 reference statements)

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“…[78] Ph 2 SO/Tf 2 O has been employed successfully for the synthesis of challenging sialic acid glycosides [79] and hyaluronic acid oligomers. [80] Recently, another powerful system, namely Me 2 S 2 /Tf 2 O, was developed for the activation of thioglycosides. [81] An important feature of these sulfinyl systems is their capacity to preactivate thioglycosides at low temperatures.…”

Section: Thioglycosidesmentioning

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: Thioglycosidesmentioning

confidence: 99%

New Principles for Glycoside‐Bond Formation

2009

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“…More recently, there has been a growing interest in the use of diphenyl sulfoxide and triflic anhydride as a system for activating glycosyl donors 6. For example, glycosyl hemiacetals can be activated directly using this combination of reagents;6, 7 glycals can be oxidised to glycosyl epoxides for reaction with alcohols;8 and this method is also often used to activate thioglycosides 4f, 7d, 9…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Studies on a Sulfoxide Transfer Reaction Mediated by Diphenyl Sulfoxide/Triflic Anhydride

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Mandal

et al. 2012

Chemistry A European J

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Sulfoxides are frequently used in organic synthesis as chiral auxiliaries and reagents to mediate a wide variety of chemical transformations. For example, diphenyl sulfoxide and triflic anhydride can be used to activate a wide range of glycosyl donors including hemiacetals, glycals and thioglycosides. In this way, an alcohol, enol or sulfide is converted into a good leaving group for subsequent reaction with an acceptor alcohol. However, reaction of diphenyl sulfoxide and triflic anhydride with oxathiane-based thioglycosides, and other oxathianes, leads to a different process in which the thioglycoside is oxidised to a sulfoxide. This unexpected oxidation reaction is very stereoselective and proceeds under anhydrous conditions in which the diphenyl sulfoxide acts both as oxidant and as the source of the oxygen atom. Isotopic labelling experiments support a reaction mechanism that involves the formation of oxodisulfonium (S-O-S) dication intermediates. These intermediates undergo oxygen-exchange reactions with other sulfoxides and also allow interconversion of axial and equatorial sulfoxides in oxathiane rings. The reversibility of the oxygen-exchange reaction suggests that the stereochemical outcome of the oxidation reaction may be under thermodynamic control, which potentially presents a novel strategy for the stereoselective synthesis of sulfoxides.

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“…[37][38][39][40][41] Hyaluronic acid is a linear GAG featuring the β-(1Ǟ3)-linked, 2-acetamido-2-deoxy--glucose-β-(1Ǟ4)--glucuronic acid disaccharide as the repeating unit. [42][43][44] The synthesis of GAG oligosaccharide sequences is crucial for the establishment of specific structure-activity relationships in order to elucidate the role of these complex sugars in nature.…”

Section: Resultsmentioning

confidence: 99%

Polymer‐Supported Synthesis of Oligosaccharides Using a Diisopropylsiloxane Linker and Trichloroacetimidate Donors

2010

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We describe herein the polymer‐supported synthesis of biologically relevant oligosaccharides using a diisopropylsiloxane linker and trichloroacetimidates as glycosyl donors. Siloxane linkers offer important advantages over closely related silyl ethers since even sterically hindered alcohols can be directly loaded onto commercially available polymers, such as soluble polyethylene glycol (PEG), without prior manipulation of the support. Final products can be easily detached by mild fluoridolysis to afford OH‐tagged sugar probes. We followed an acceptor‐bound approach that fixed the nucleophile on the polymer, and we selected soluble PEG as the support due to higher reactivity of bound sugars and easy reaction monitoring. Following this strategy, the trisaccharide repeating unit of the capsular polysaccharide of Neisseria meningitidis (serogroup L) and the disaccharide containing the structural motif of hyaluronic acid were successfully synthesized.

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Synthesis of Hyaluronic Acid Oligomers Using Ph₂SO/Tf₂O-Mediated Glycosylations

Abstract: The synthesis of hyaluronic acid (HA) oligomers using a stepwise glycosylation strategy is described. This method employs protected 1-hydroxyuronic acid and 1-phenylthio glucosamine donors, both of which are activated with the Ph2SO/Tf2O activator system.

Cited by 42 publications

References 15 publications

New Principles for Glycoside‐Bond Formation

New Principles for Glycoside‐Bond Formation

Mechanistic Studies on a Sulfoxide Transfer Reaction Mediated by Diphenyl Sulfoxide/Triflic Anhydride

Polymer‐Supported Synthesis of Oligosaccharides Using a Diisopropylsiloxane Linker and Trichloroacetimidate Donors

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Synthesis of Hyaluronic Acid Oligomers Using Ph2SO/Tf2O-Mediated Glycosylations

Abstract: The synthesis of hyaluronic acid (HA) oligomers using a stepwise glycosylation strategy is described. This method employs protected 1-hydroxyuronic acid and 1-phenylthio glucosamine donors, both of which are activated with the Ph2SO/Tf2O activator system.

Cited by 42 publications

References 15 publications

New Principles for Glycoside‐Bond Formation

New Principles for Glycoside‐Bond Formation

Mechanistic Studies on a Sulfoxide Transfer Reaction Mediated by Diphenyl Sulfoxide/Triflic Anhydride

Polymer‐Supported Synthesis of Oligosaccharides Using a Diisopropylsiloxane Linker and Trichloroacetimidate Donors

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Synthesis of Hyaluronic Acid Oligomers Using Ph₂SO/Tf₂O-Mediated Glycosylations