Glycosylation Methods in Oligosaccharide Synthesis. Part 1

Robina, Inmaculada; Carmona, Ana T.; Vargas, Ângelo

doi:10.2174/157017908783497545

Cited by 10 publications

(1 citation statement)

References 89 publications

(103 reference statements)

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“…Glycosylation, the formation of a new glycosidic bond between two sugar units, has remained the central reaction in carbohydrate synthesis. Since the first report on glycoside synthesis by Michael in 1879 and Fischer glycosylation in 1893, followed by the advent of the Koenigs–Knorr reaction in 1901, glycosylation has undergone many changes over the years. ,− Glycosylation is probably the most intriguing reaction that has mesmerized the carbohydrate community for such a long time. In contrast to the synthesis of other biomolecules such as proteins and nucleic acids, wherein no regio or stereochemical issues are involved in the coupling step, sugar coupling has to be controlled such that only one of several reactive hydroxyl groups is coupled with the other partner and with the desired stereoselectivity (α or β).…”

Section: Glycosylationmentioning

confidence: 99%

“One-Pot” Protection, Glycosylation, and Protection–Glycosylation Strategies of Carbohydrates

et al. 2018

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Carbohydrates, which are ubiquitously distributed throughout the three domains of life, play significant roles in a variety of vital biological processes. Access to unique and homogeneous carbohydrate materials is important to understand their physical properties, biological functions, and disease-related features. It is difficult to isolate carbohydrates in acceptable purity and amounts from natural sources. Therefore, complex saccharides with well-defined structures are often most conviently accessed through chemical syntheses. Two major hurdles, regioselective protection and stereoselective glycosylation, are faced by carbohydrate chemists in synthesizing these highly complicated molecules. Over the past few years, there has been a radical change in tackling these problems and speeding up the synthesis of oligosaccharides. This is largely due to the development of one-pot protection, one-pot glycosylation, and one-pot protection-glycosylation protocols and streamlined approaches to orthogonally protected building blocks, including those from rare sugars, that can be used in glycan coupling. In addition, new automated strategies for oligosaccharide syntheses have been reported not only for program-controlled assembly on solid support but also by the stepwise glycosylation in solution phase. As a result, various sugar molecules with highly complex, large structures could be successfully synthesized. To summarize these recent advances, this review describes the methodologies for one-pot protection and their one-pot glycosylation into the complex glycans and the chronological developments associated with automated syntheses of oligosaccharides.

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Section: Glycosylationmentioning

confidence: 99%

“One-Pot” Protection, Glycosylation, and Protection–Glycosylation Strategies of Carbohydrates

et al. 2018

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Do Glycosyl Sulfonium Ions Engage in Neighbouring‐Group Participation? A Study of Oxathiane Glycosyl Donors and the Basis for their Stereoselectivity

Fascione

Kilner

Leach

et al. 2011

Chemistry A European J

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Neighbouring-group participation has long been used to control the synthesis of 1,2-trans-glycosides. More recently there has been a growing interest in the development of similar strategies for the synthesis of 1,2-cis-glycosides, in particular the use of auxiliary groups that generate sulfonium ion intermediates. However, there has been some debate over the role of sulfonium ion intermediates in these reactions: do sulfonium ions actually engage in neighbouring-group participation, or are they a resting state of the system prior to reaction through an oxacarbenium ion intermediate? Herein, we describe the reactivities and stereoselectivities of a family of bicyclic thioglycosides in which an oxathiane ring is fused to the sugar to form a trans-decalin-like structure. A methyl sulfonium ion derived from one such glycosyl donor is so stable that it can be crystallised from ethanol, yet it reacts with complete stereoselectivity at high temperature. The importance of a ketal group in the oxathiane ring for maintaining this high stereoselectivity is investigated using a combination of experiment and ab initio calculations. The data are discussed in terms of S(N)1 and S(N)2 type mechanisms. Trends in stereoselectivity across a series of compounds are more consistent with selective addition to oxacarbenium ions rather than a shift between S(N)1 and S(N)2 mechanisms.

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Light Scattering in Non-aqueous Solutions of Low-Molecular-Mass Compounds: Application for Supramer Analysis of Reaction Solutions

et al. 2020

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Glycosylation Methods in Oligosaccharide Synthesis. Part 1

Cited by 10 publications

References 89 publications

“One-Pot” Protection, Glycosylation, and Protection–Glycosylation Strategies of Carbohydrates

“One-Pot” Protection, Glycosylation, and Protection–Glycosylation Strategies of Carbohydrates

Do Glycosyl Sulfonium Ions Engage in Neighbouring‐Group Participation? A Study of Oxathiane Glycosyl Donors and the Basis for their Stereoselectivity

Light Scattering in Non-aqueous Solutions of Low-Molecular-Mass Compounds: Application for Supramer Analysis of Reaction Solutions

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