Comparing n-pentenyl orthoesters and n-pentenyl glycosides as alternative glycosyl donors

Mach, Mateusz; Schlueter, Urs; Mathew, Felix; Fraser‐Reid, Bert; Hazen, Kevin C.

doi:10.1016/s0040-4020(02)00671-3

Cited by 77 publications

(46 citation statements)

References 31 publications

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“…Results of Fraser-Reid and co-workers with n-pentenylorthoesters (NPOEs) may change this view. [113] However, NPOE activation requires at least an equimolar amount of a pentenylgroup-activating reagent.…”

Section: 2-orthoesters Of Aldosesmentioning

confidence: 99%

“…[114] Soon these orthoesters derived from pentenyl alcohols were investigated thoroughly as glycosyl donors with different promoters and acceptors. [113] A major advantage of these donors is that activation with NIS leads through reaction with the iodonium ion to the liberation of the pentenyl moiety as iodomethyltetrahydrofuran, which can therefore not compete with the acceptor with respect to the formation of the glycosidic bond.…”

Section: 2-orthoesters Of Aldosesmentioning

confidence: 99%

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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: 2-orthoesters Of Aldosesmentioning

confidence: 99%

Section: 2-orthoesters Of Aldosesmentioning

confidence: 99%

New Principles for Glycoside‐Bond Formation

2009

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“…The synthesis of n -pentenyl trimannoside 60 relied on sequential Koenigs–Knorr glycosylations using mannose monomers 63–65 , which were all prepared from the n -pentenyl orthoester 73 70 68 (Scheme 12). This intermediate allowed for ready conversion into 2- O -benzoyl-protected donors, thus facilitating α-stereoselective glycosylations and flexibility with regard to choice of leaving group at the anomeric position.…”

Section: Classic Approaches To Gpi Synthesismentioning

confidence: 99%

“…In contrast to Guo’s early-stage phospholipidation to avoid a side reaction, Fraser-Reid disconnected the target to pseudopentasaccharide 178 , which after introduction of phosphoethanolamine would undergo late-stage acylation at O-2 of the inositol and phospholipidation at O-1 via an intermediate orthoester. The preparation of 178 made use of a linear assembly strategy involving consecutive mannosylations of pseudodisaccharide 181 with n -pentenyl orthoester (NPOE) 73 building blocks 182 , 72 , and 183 . A novel strategy was developed to enhance the α-stereoselectivity in the formation of pseudodisaccharide 181 .…”

Section: Classic Approaches To Gpi Synthesismentioning

confidence: 99%

Chemical Synthesis of Glycosylphosphatidylinositol Anchors

Swarts

Guo

2012

Advances in Carbohydrate Chemistry and Biochemistry

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Many eukaryotic cell-surface proteins and glycoproteins are anchored to the plasma membrane by glycosylphosphatidylinositols (GPIs), a family of glycolipids that are post-translationally attached to proteins at their C-termini. GPIs and GPI-anchored proteins play important roles in many biological and pathological events, such as cell recognition and adhesion, signal transduction, host defense, and acting as receptors for viruses and toxins. Chemical synthesis of structurally defined GPI anchors and GPI derivatives is a necessary step toward understanding the properties and functions of these molecules in biological systems and exploring their potential therapeutic applications. In the first part of this comprehensive article on the chemical synthesis of GPIs, classic syntheses of naturally occurring GPI anchors from protozoan parasites, yeast, and mammals are covered. The second part of the article focuses on recent diversity-oriented strategies for the synthesis of GPI anchors containing unsaturated lipids, “click chemistry” tags, and highly branched and modified structures.

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“…Thereafter, isomerization of lactosyl propargyl 1,2-orthoacetate 3 to propargyl lactoside (4) with a O-acetyl group at C-2 position was achieved efficiently in 85 % yield by the use of a catalytic amount of TMSOTf and propargyl alcohol in anhydrous CH 2 Cl 2 at room temperature for 15 min (Supporting Information [52]). Propargyl lactoside 4 was then treated with a solution of sodium methoxide in anhydrous methanol to deprotect acetate group and thus obtained equatorial alcohol 5 was oxidized under conditions DMSO/Ac 2 O/25°C/24 h followed by reduction with sodium borohydride in a mixture of anhydrous CH 2 Cl 2 and CH 3 OH (1:1) to obtain the required disaccharide acceptor (6) in 82 % yield (Scheme 2) ( [28,53,54] Supporting Information).…”

mentioning

confidence: 99%

AuBr3 mediated glycosidations: synthesis of tetrasaccharide motif of the Leishmania donovani lipophosphoglycan

Sureshkumar

Hotha

2012

Glycoconj J

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Tetrasaccharide cap present in lipophosphoglycan of the Leishmania donovani responsible for visceral Leishmaniaisis is synthesized as a fully protected propargyl glycoside. AuBr(3) mediated selective glycosylation of propargyl 1,2-orthoester in the presence of propargyl glycoside is employed as a key step to obtain propargyl containing oligomers. Further, propargyl tetrasaccharide is connected with a long chain hydrocarbon containing azidothiol functionality situated at two terminal ends via 'click' reaction.

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Comparing n-pentenyl orthoesters and n-pentenyl glycosides as alternative glycosyl donors

Cited by 77 publications

References 31 publications

New Principles for Glycoside‐Bond Formation

New Principles for Glycoside‐Bond Formation

Chemical Synthesis of Glycosylphosphatidylinositol Anchors

AuBr3 mediated glycosidations: synthesis of tetrasaccharide motif of the Leishmania donovani lipophosphoglycan

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