De Novo Asymmetric Bio- and Chemocatalytic Synthesis of Saccharides − Stereoselective Formal <i>O</i>-Glycoside Bond Formation Using Palladium Catalysis

Comely, Alex C.; Eelkema, Rienk; Minnaard, Adriaan J.; Feringa, Ben L.

doi:10.1021/ja0347538

Cited by 108 publications

(53 citation statements)

References 26 publications

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“…Much effort has also been directed towards a conceptually different glycosylation method, namely, the de novo synthesis of glycosides, although this method was investigated extensively and successfully many years ago. [310] In recent studies, [311] the glycoside bonds were constructed through palladium-catalyzed allylation, and the anomeric configuration could be controlled by the reagent rather than by anomeric or neighboring-group effects. The glycosylation usually proceeded in a highly stereoselective manner without the use of Lewis acid promoters, and the products could be elaborated readily to furnish natural or non-natural carbohydrates.…”

Section: Other Aspectsmentioning

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: Other Aspectsmentioning

confidence: 99%

New Principles for Glycoside‐Bond Formation

2009

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“…8−11 2,3-Unsaturated pyranosides can also be synthesized de novo by the Pd-catalyzed acetalization of chiral pyranones followed by post-glycosylative reduction and dihydroxylation to produce three additional stereocenters in the newly formed hexose unit. 12,13 Similarly, 3,4-dideoxyhexenosides have been converted into S -linked disaccharides and glycoconjugates via epoxidation and S N 2 ring-opening. 14 …”

Section: Introductionmentioning

confidence: 99%

Synthesis and Reactivity of 4′-Deoxypentenosyl Disaccharides

et al. 2014

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4-Deoxypentenosides (4-DPs) are versatile synthons for rare or higher-order pyranosides, and they provide an entry for structural diversification at the C5 position. Previous studies have shown that 4-DPs undergo stereocontrolled DMDO oxidation; subsequent epoxide ring-openings with various nucleophiles can proceed with both anti or syn selectivity. Here, we report the synthesis of α- and β-linked 4′-deoxypentenosyl (4′-DP) disaccharides, and we investigate their post-glycosylational C5′ additions using the DMDO oxidation/ring-opening sequence. The α-linked 4′-DP disaccharides were synthesized by coupling thiophenyl 4-DP donors with glycosyl acceptors using BSP/Tf2O activation, whereas β-linked 4′-DP disaccharides were generated by the decarboxylative elimination of glucuronyl disaccharides under microwave conditions. Both α- and β-linked 4′-DP disaccharides could be epoxidized with high stereoselectivity using DMDO. In some cases, the α-epoxypentenosides could be successfully converted into terminal l-iduronic acids via the syn addition of 2-furylzinc bromide. These studies support a novel approach to oligosaccharide synthesis, in which the stereochemical configuration of the terminal 4′-DP unit is established at a post-glycosylative stage.

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“…In recent studies, three groups have independently reported the application of the Tsuji-Trost reaction to the construction of glycoside bonds [181]. These transformations proceed with good levels of stereocontrol and allow for catalyst-based control of anomeric stereochemistry (eq 118) [181c].…”

Section: Heterocycle Synthesis Via the Tsuji-trost Reactionmentioning

confidence: 99%