Unsaturated Sugars: A Rich Platform for Methodological and Synthetic Studies

Fraser‐Reid, Bert; López, J. Cristóbal

doi:10.2174/138527209787847363

Cited by 23 publications

(12 citation statements)

References 112 publications

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“…Excellent coverage of the chemistry and synthetic applications of hex-2-enopyranosides has appeared regularly in the yearly issues of Carbohydrate Chemistry, Specialist Periodical Reports , until 2003 [11]. The vast contribution to the chemistry of hex-2-eno-pyranosides developed in the Fraser-Reid group, covering more than 20 years of research in the area, has recently been reviewed [12].…”

Section: Introductionmentioning

confidence: 99%

A Survey of Recent Synthetic Applications of 2,3-Dideoxy-Hex-2-enopyranosides

et al. 2015

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Section: Introductionmentioning

confidence: 99%

A Survey of Recent Synthetic Applications of 2,3-Dideoxy-Hex-2-enopyranosides

et al. 2015

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“… , In this reaction, the C3-acetyl group in fully acetylated glycals is cleaved to form the “Ferrier” glycosyl cation that in turn is attacked by nucleophiles at the C1 position. After an allylic shift, the reaction yields 2,3-unsaturated glycosides, a class of glycosides that is relevant for the synthesis of natural products and pharmaceuticals such as 2-deoxyglycosides, C-glycopyranosyl arenes, and heteroarenes . The reaction can also be observed for glycals bearing other participating protecting groups, i.e., benzoyl …”

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confidence: 99%

Direct Experimental Characterization of the Ferrier Glycosyl Cation in the Gas Phase

et al. 2020

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The Ferrier rearrangement reaction is crucial for the synthesis of pharmaceuticals. Although its mechanism was described more than 50 years ago, the structure of the intermediate remains elusive. Two structures have been proposed for this Ferrier glycosyl cation: a 1,2-unsaturated cation that is resonance-stabilized within the pyranose ring or a cation that is stabilized by the anchimeric assistance of a neighboring acetyl group. Using a combination of gas-phase cryogenic infrared spectroscopy in helium nanodroplets and first-principles density functional theory, we provide the first direct structural characterization of Ferrier cations. The data show that both acetylated glucal and galactal lead to glycosyl cations of the dioxolenium type.

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“…The O-allyl product 3 in toluene (4 mL) was heated at 165 °C in a sealed tube for over 45 min, and solvents were removed in vacuo to afford 2 (0.56 g, 63%) (α/β = 1.2:1) as an oil: IR 1738 cm −1 . 1 3-C-(3′,4′,6′-Tri-O-benzyl-2-deoxy-2-C-methylene-α/β-D-arabino-hexopyranosyl)propene (4 and 5). n BuLi (1.6 M hexane) (1.47 mL, 2.36 mmol) was added dropwise to a solution of Ph 3 PMeI (1.2 g, 2.96 mmol) in THF (10 mL) at 0 °C.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Synthesis of 2-Deoxy-2-C-alkyl Glycal and Glycopyranosides from 2-Hydroxy Glycal Ester

Daskhan

Jayaraman

2012

J. Org. Chem.

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A method to convert 2-hydroxy glycal ester to the corresponding 2-deoxy-2-C-alkyl glycal in a facile manner, through key reactions including (i) C-allylation at C-1, (ii) Wittig reaction, and (iii) Cope rearrangement of a 1,5-diene derivative, is reported. The α-anomer of the 1,5-diene derivative underwent Cope rearrangement to afford 2-deoxy-2-C-glycal derivative, whereas the β-anomer was found to be unreactive. Employing this sequence, 3,4,6-tri-O-benzyl-2-O-acetyl-1,5-anhydro-d-arabino-hex-1-enitol was transformed to 3,4,6-tri-O-benzyl-2-deoxy-2-C-alkyl-1,5-anhydro-D-arabino-hex-1-enitol. 2-Deoxy-2-C-alkyl glycal derivative is a suitable glycosyl donor to prepare 2-deoxy-2-C-alkyl glycosides, mediated through haloglycosylation and a subsequent dehalogenation. A number of 2-deoxy-2-C-alkyl glycosides, with both glycosyl and nonglycosyl moieties at the reducing end, are thus prepared from the glycal.

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Unsaturated Sugars: A Rich Platform for Methodological and Synthetic Studies

Cited by 23 publications

References 112 publications

A Survey of Recent Synthetic Applications of 2,3-Dideoxy-Hex-2-enopyranosides

A Survey of Recent Synthetic Applications of 2,3-Dideoxy-Hex-2-enopyranosides

Direct Experimental Characterization of the Ferrier Glycosyl Cation in the Gas Phase

Synthesis of 2-Deoxy-2-C-alkyl Glycal and Glycopyranosides from 2-Hydroxy Glycal Ester

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