Unusual promoters and leaving groups in glycosylation reactions: The evolution of carbohydrate synthesis

Morelli, Laura; Compostella, Federica; Panza, Luigi; Imperio, Daniela

doi:10.1016/j.carres.2022.108625

Cited by 6 publications

(3 citation statements)

References 112 publications

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“…Much effort has focused on the anomeric leaving group, leading to the development of a range of glycosylating agents. [250][251][252][253][254][255][256] Here, six major approaches for glycoside synthesis are discussed:…”

Section: Commonly Used Glycosylating Agentsmentioning

confidence: 99%

Advances in glycoside and oligosaccharide synthesis

Crawford,

Seeberger

2023

Chem. Soc. Rev.

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Section: Commonly Used Glycosylating Agentsmentioning

confidence: 99%

Advances in glycoside and oligosaccharide synthesis

Crawford,

Seeberger

2023

Chem. Soc. Rev.

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“…Controlling the stereoselectivity in the formation of 1,2-cis glycosides is extremely challenging in synthetic chemistry, as in the case of α-gluco (2-equatorial)-and β-manno (2-axial)-type glycoside formations, although the method for the 1,2-trans isomers was developed by using the effect of neighboring group participation from theC-2 acyl group as the first choice of the chemist. Various methods using inter- [150][151][152][153][154][155] and intra- [156][157][158] molecular procedures have been developed for the stereoselective synthesis of 1,2cis glycosides [153,159], depending on the acceptor molecules [160,161], and further developments have been reported in recent years [162][163][164][165].…”

Section: 2-cis Glycosylationmentioning

confidence: 99%

Recent Progress in 1,2-cis glycosylation for Glucan Synthesis

et al. 2023

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Controlling the stereoselectivity of 1,2-cis glycosylation is one of the most challenging tasks in the chemical synthesis of glycans. There are various 1,2-cis glycosides in nature, such as α-glucoside and β-mannoside in glycoproteins, glycolipids, proteoglycans, microbial polysaccharides, and bioactive natural products. In the structure of polysaccharides such as α-glucan, 1,2-cis α-glucosides were found to be the major linkage between the glucopyranosides. Various regioisomeric linkages, 1→3, 1→4, and 1→6 for the backbone structure, and 1→2/3/4/6 for branching in the polysaccharide as well as in the oligosaccharides were identified. To achieve highly stereoselective 1,2-cis glycosylation, including α-glucosylation, a number of strategies using inter- and intra-molecular methodologies have been explored. Recently, Zn salt-mediated cis glycosylation has been developed and applied to the synthesis of various 1,2-cis linkages, such as α-glucoside and β-mannoside, via the 1,2-cis glycosylation pathway and β-galactoside 1,4/6-cis induction. Furthermore, the synthesis of various structures of α-glucans has been achieved using the recent progressive stereoselective 1,2-cis glycosylation reactions. In this review, recent advances in stereoselective 1,2-cis glycosylation, particularly focused on α-glucosylation, and their applications in the construction of linear and branched α-glucans are summarized.

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“…Carbohydrates are diverse biomolecules that are implicated in multiple natural processes, such as protein folding, intracellular communication, and bacterial pathogenesis. , Much work in recent years has been devoted to the production of O-linked glycans as new therapeutics and glycobiological probes, − but the reactivity of O linkages to acid hydrolysis and enzymatic degradation can hinder the efficacy of these products in vivo . One way to address this issue is to replace the oxygen linkage with a methylene unit, which can increase the stability of therapeutic glycans without compromising their biological activity. − For example, alkyl exo - C -glycoside derivatives of KRN-7000, an immunostimulatory galactosyl ceramide derivative of sponge Agelas mauritianus glycolipid extracts (Figure ), were found to better activate natural killer T-cells against murine melanoma than O -glycoside derivatives at similar doses. , Alkyl C -glycosides have also been evaluated as competitive antagonists of DC-SIGN, a dendritic cell C-type lectin specific for l -fucose and d -mannose residues located in Le x antigen and high-mannose-containing viral glycoproteins, respectively .…”

mentioning

confidence: 99%

Application of Redox-Active Ester Catalysis to the Synthesis of Pyranose Alkyl C-Glycosides

Romeo,

Lucera,

Jensen

et al. 2023

Org. Lett.

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The direct coupling of shelf-stable, tetrachloro-N-hydroxyphthalimide ester (TCNHPI) glycosyl donors with a variety of alkylzinc reagents under redox catalysis is described. Alkyl C-glycosides are formed directly by a decarboxylative, Negishi-type process in 31–73% yields without the need for photocatalytic activation or additional reductants. Extension of this approach to the coupling of TCNHPI donors with stereodefined α-alkoxy furan-containing alkylzinc halides enabled de novo synthesis of methylene-linked exo-C-disaccharides via an Achmatowicz rearrangement.

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Unusual promoters and leaving groups in glycosylation reactions: The evolution of carbohydrate synthesis

Cited by 6 publications

References 112 publications

Advances in glycoside and oligosaccharide synthesis

Advances in glycoside and oligosaccharide synthesis

Recent Progress in 1,2-cis glycosylation for Glucan Synthesis

Application of Redox-Active Ester Catalysis to the Synthesis of Pyranose Alkyl C-Glycosides

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