Oligosaccharide Synthesis and Translational Innovation

Krasnova, Larissa B.; Wong, Chi‐Huey

doi:10.1021/jacs.8b11005

Cited by 147 publications

(97 citation statements)

References 323 publications

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“…Because these diastereoisomers have different physical and biochemical properties, glycoside bond stereochemistry has been called the "central topic" of synthetic carbohydrate chemistry. 3 Most synthetic glycosylations involve the addition of a nucleophilic alcohol (acceptor) to a carbohydrate electrophile (donor, Fig. 1A) and lie along a continuum bound by SN1 and SN2 pathways.…”

Section: Textmentioning

confidence: 99%

Programmable Synthesis of 2-Deoxyglycosides

2019

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Control of glycoside bond stereochemistry is the central challenge in the synthesis of oligosaccharides. 2-Deoxyglycosides, which lack a C2 substituent to guide stereoselectivity, are among the most difficult classes of glycoside bond constructions. Here we present a method to synthesize 2-deoxysaccharides with specified glycoside bond stereochemistry using a nucleophilic carbohydrate residue and the synthetic equivalent of an alcohol electrophile.Because the configuration of the nucleophile can be precisely controlled, both αand βglycosides can be synthesized from the same starting material in nearly all cases examined.Stereoselectivities in these reactions are often greater than 50:1 and yields typically exceed 70%.This strategy is amenable to the stereocontrolled syntheses of trisaccharide diastereomers, and a tetrasaccharide. Our method offers a fundamentally new approach to O-glycoside synthesis to enable downstream biochemical and natural product applications.

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Section: Textmentioning

confidence: 99%

Programmable Synthesis of 2-Deoxyglycosides

2019

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“…Moreover, a detailed structural investigation of such compounds is often missing. Compared to peptide synthesis, the synthesis of oligo‐ and polysaccharides is more challenging, requiring complex protecting group strategies and precise control over reaction conditions . Nevertheless, chemical synthesis remains the only alternative to achieve full control over the oligosaccharide sequence, providing a tool for single‐site modifications.…”

Section: Helical Stabilizationmentioning

confidence: 99%

Helical polysaccharides

2019

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In analogy to polypeptides and polynucleotides, polysaccharides tend to form helical secondary structures, as well as higher hierarchical assemblies. Nevertheless, the conformation of polysaccharides in solution remains in most cases elusive due to their intrinsic complexity and lack of analytical techniques. In this review, we discuss the different helical shapes adopted by polysaccharides, with particular focus on how the helical character is exploited to form supramolecular assemblies, such as inclusion complexes with linear guest molecules and co‐helices with polynucleotide strands. Several methodologies are used to tune the polysaccharides conformation, ranging from ion‐mediated coil‐helix transition to chemical synthesis of well‐defined compounds with specific modifications. The latter provides ideal tailor‐made probes for structural studies, with the aim to correlate their three‐dimensional structure and the macroscopic properties. Applications of oligosaccharides with defined shapes in molecular recognition and catalysis are envisioned.

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“…With the recent advancement of analytical technologies, e.g., mass spectrometry, nuclear magnetic resonance spectroscopy and uorescence microscopy, it has become possible to gain insights into the structure of glycans. A combination of these technologies with tools like cell surface glycan engineering, 14,15 chemical and enzymatic glycan assembly 16,17 and genetic engineering 18 has been proven to be powerful for revealing the composition of the cell glycocalyx. However, dening the functional roles of spatial organization and mobility of glycans towards their biological activity has been limited.…”

Section: Introductionmentioning

confidence: 99%