Unexpected fluorous solvent effect on oxidation of 1-thioglycosides

Misbahi, K.; Lardic, Morgane; Ferrières, Vincent; Noiret, Nicolas; Kerbal, Abdelali; Plusquellec, Daniel

doi:10.1016/s0957-4166(01)00437-2

Cited by 10 publications

(2 citation statements)

References 21 publications

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“…It has recently been assumed that the oxidation of β-thioglycosides in the gluco, galacto and mano series always give the sulfoxides with S absolute configuration majoritarly . Our actual results, as well as those recently reported by Ferrieres and Plusquellec, indicate that the oxidation of β-thioglycosides depends not only on the configuration of C-2, but also on the nature of the protective group. To get better insight in the stereochemical outcome of the oxidation, iminothioglycosides with a bulky pivaloyl protective group were planned and synthesized as before.…”

Section: Resultssupporting

confidence: 82%

Highly Diastereoselective Oxidation of 2-Amino-2-deoxy-1-thio-β-d-glucopyranosides: Synthesis of Imino Sulfinylglycosides

et al. 2003

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A synthetic route to imino thioglycosides and to imino sulfinylglycosides has been developed. A detailed study on the diastereoselective oxidation of 2-amino-2-deoxy-1-thio-beta-D-glucopyranosides is reported. It has been shown that the stereochemical outcome of the oxidation is highly dependent on the protective group of the amine function. While the oxidation of iminothioglycosides is slightly diastereoselective (up to 30% de in favor of the R(S) sulfoxide), a single isomer is obtained in the case of tetrachlorophthalimido derivatives. The absolute configuration of the sulfinyl glycoside was ascertained by NMR analysis using our recent model on the basis of the exo-anomeric effect corroborated by X-ray crystallography.

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Section: Resultssupporting

confidence: 82%

Highly Diastereoselective Oxidation of 2-Amino-2-deoxy-1-thio-β-d-glucopyranosides: Synthesis of Imino Sulfinylglycosides

et al. 2003

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“…Moreover, fluorous solvents could engage in diverse weak interactions such as π–π F , C–F···H hydrogen bond, C–F···C=O, and anion-π F , which play essential roles in the promotion of chemical transformations by enhancing reactivity and stereoselectivity as well as the design of functional materials [ 26 , 27 , 37 , 38 , 39 , 40 , 41 ]. In carbohydrate chemistry, it has been found that introducing a perfluorinated solvent could improve the reaction outcome [ 42 , 43 , 44 , 45 ]. These findings led us to postulate that the weak interactions stemming from perfluorinated solvent could be leveraged to improve the acid-catalyzed Ferrier-type glycosylation reaction ( Figure 1 d).…”

Section: Introductionmentioning

confidence: 99%

Acid Catalyzed Stereocontrolled Ferrier-Type Glycosylation Assisted by Perfluorinated Solvent

Yanzhi

Xiang

et al. 2022

Molecules

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Described herein is the first application of perfluorinated solvent in the stereoselective formation of O-/S-glycosidic linkages that occurs via a Ferrier rearrangement of acetylated glycals. In this system, the weak interactions between perfluoro-n-hexane and substrates could augment the reactivity and stereocontrol. The initiation of transformation requires only an extremely low loading of resin-H+ and the mild conditions enable the accommodation of a broad spectrum of glycal donors and acceptors. The ‘green’ feature of this chemistry is demonstrated by low toxicity and easy recovery of the medium, as well as operational simplicity in product isolation.

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Glycosylation with Sulfoxides and Sulfinates as Donors or Promoters

Crich

Lim

2004

Organic Reactions

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The efficient, stereocontrolled formation of glycosidic bonds is arguably the most fundamental reaction in glycoscience. This chapter surveys four recent distinct glycosylation methods united by the common theme of employing sulfoxides, or closely related sulfinates, either in the glycosyl donor itself or as an integral part of the promoter. In the first method (the sulfoxide method), a glycosyl sulfoxide, the donor, is coupled to an acceptor alcohol by means of an activating agent to give the glycosidic bond. The activating agent is typically triflic anhydride, but other compounds have been used. In the second method (the thiogylcoside method) the donor is thioglycoside. It is activated by means of a promoter derived from the reaction of trifluoromethanesulfonic anhydride and thiosulfinate, a sulfinaminde, or diphenylsulfoxide before coupling to an acceptor alcohol. The third method is dehydrative coupling. This chapter is concerned only with the recent variations in which dehydration is achieved by means of a combination of diaryl sulfoxides and trifluoromethanesulfonic acid. The last method (the oxidative method), involves the direct oxidative glycosylation of glycals. This method differs significantly from the other methods since it does not employ a traditional anomeric derivative as glycosly donor, but derives one from the formal oxidation of glycal. At some time in the activation process, all four methods typically involve the reaction of a sulfoxide, or sulfinate with trifluoromethanesulfonic anhydride. All four methods possess the distinct advantage of using readily prepared, stable gylcosyl donors. Three of them are metal‐free and two of them are capable of coupling to enable the most hindered unreactive alcohols in a matter of minutes at low temperature. These methods are some of the most powerful available for the formation of glycosidic linkages.

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Unexpected fluorous solvent effect on oxidation of 1-thioglycosides

Cited by 10 publications

References 21 publications

Highly Diastereoselective Oxidation of 2-Amino-2-deoxy-1-thio-β-d-glucopyranosides: Synthesis of Imino Sulfinylglycosides

Highly Diastereoselective Oxidation of 2-Amino-2-deoxy-1-thio-β-d-glucopyranosides: Synthesis of Imino Sulfinylglycosides

Acid Catalyzed Stereocontrolled Ferrier-Type Glycosylation Assisted by Perfluorinated Solvent

Glycosylation with Sulfoxides and Sulfinates as Donors or Promoters

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