A Highly Stereoselective Synthesis of α-Glucosides from 1-<i>O</i>-Acetyl Glucose by Use of Tin(IV) Chloride–Silver Perchlorate Catalyst System

Mukaiyama, Teruaki; Takashima, Tohru; Katsurada, Manabu; Aizawa, Hiroyuki

doi:10.1246/cl.1991.533

Cited by 54 publications

(11 citation statements)

References 15 publications

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“…Various glucosylation methods have been developed since the classical KoenigsKnorr synthesis. 3 Usually, these procedures require either an activated glucosyl donor, e.g., a glucosyl halide, 4,5 trimethylsilyl 2,3,4,6-tetra-O-acetyl-D-glucopyranoside, 6 or a trichloroacetimidate, 7,8 a glucosyl acceptor with a good leaving group [9][10][11] or a precious metal catalyst. 12,13 Glucosylation can also be performed enzymically; 14 the unprotected monosaccharide is derivatized in a water-poor system using the glucosyl acceptor (e.g., allyl or benzyl alcohol) as the solvent.…”

Section: Introductionmentioning

confidence: 99%

Reliable method for the synthesis of aryl β-D-glucopyranosides, using boron trifluoride–diethyl ether as catalyst

Smits¹,

Engberts²,

Kellogg³

et al. 1996

J. Chem. Soc., Perkin Trans. 1

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Reliable method for the synthesis of aryl β-D-glucopyranosides, using boron trifluoride-diethyl ether as catalyst Smits, Elly; Engberts, Jan; Kellogg, Richard M.; Doren, Henk A. van Take-down policy If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.Downloaded from the University of Groningen/UMCG research database (Pure): http://www.rug.nl/research/portal. For technical reasons the number of authors shown on this cover page is limited to 10 maximum. Stereospecific formation of aryl 2,3,4,6-tetra-O-acetyl-β β-D-glucopyranosides was achieved by reaction of penta-O-acetyl-β β-D-glucose 1 with substituted phenols in the presence of boron trifluoride. Yields of the purified products varied from 52-85%. Benzyl alcohol could also be glucosylated using similar conditions. All products were purified by crystallization from ethanol. The purity and the anomeric configuration of the products were determined by means of 1 H and 13 C NMR spectroscopy, melting points and optical rotation.

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Section: Introductionmentioning

confidence: 99%

Reliable method for the synthesis of aryl β-D-glucopyranosides, using boron trifluoride–diethyl ether as catalyst

Smits¹,

Engberts²,

Kellogg³

et al. 1996

J. Chem. Soc., Perkin Trans. 1

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“…The perchlorate ion prefers to stay on the less-hindered β face of the ion, and therefore the nucleophile attacks the α face preferentially. [18] The presence of the fluorine atom could affect the stereochemical outcome of the reaction in two (nonmutually exclusive) ways − steric and electronic. On one hand, the limited steric hindrance of the fluorine atom (much smaller than any protected OH group, including OCH 3 ) would allow the perchlorate ion to stay on both faces of the cation, thus allowing the nucleophile to attack both sides.…”

Section: Resultsmentioning

confidence: 99%

Immunomodulatory α‐Galactoglycosphingolipids: Synthesis of 2'‐Fluoro‐2'‐deoxy‐α‐galactosylceramide and an Evaluation of Its Immunostimulating Properties

et al. 2005

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In the framework of a project to assess the immunomodulating properties of α‐galactosyl glycosphingolipids, the total synthesis of 1‐O‐(2‐fluoro‐2‐deoxy‐α‐D‐galactopyranosyl)‐2‐docosanoylamino‐1,3,4‐octadecanetriol (1), a 2'‐fluoro analogue of the immunostimulating α‐galactoglycosphingolipids, was accomplished. The glycosidation reaction of the azido precursor of sphingosine was performed using the Mukaiyama glycosidation reaction. The stimulation of mouse splenocyte proliferation by the 2'‐fluoro analogue was highly reduced compared to that of the α‐galactoglycosphingolipids, thereby confirming that a free galactose 2‐OH group is essential for the immunostimulatory activity. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)

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“…[11] The original Mukayama glycosidation reaction involves a glycosyl fluoride as the glycosyl donor, and AgClO 4 and SnCl 2 as a Lewis acid catalytic system. An ion pair is postulated [12] to be produced by the cationic anomeric center and the perchlorate ion, with the perchlorate ion placed on the less-hindered β face of the sugar so as to cause nucleophilic attack at the α face. Over the years, several improved versions of the original Mukayama glycosidation reaction have appeared in an attempt to improve the yield of the reaction.…”

Section: Resultsmentioning

confidence: 99%

Immunomodulatory α‐Galactoglycosphingolipids: Synthesis of a 2′‐O‐Methyl‐α‐Gal‐GSL and Evaluation of Its Immunostimulating Capacity

Barbieri¹,

Costantino²,

Fattorusso³

et al. 2004

Eur J Org Chem

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The total synthesis of 1‐2‐docosanoylamino‐O‐(2‐O‐methyl‐α‐D‐galactopyranosyl)‐1,3,4‐octadecanetriol (2), a 2′‐methoxy analog of the immunostimulating α‐galactoglycosphingolipid 1, is reported. Stereoselective α‐glycosylation of the azido precursor of sphingosine was successfully performed for the first time using an improved Mukaiyama reaction. When assayed in a 72 h splenocyte proliferation test, compound 2 was significantly less stimulatory than the non‐methylated compound 1, suggesting that the galactose 2‐OH group is essential for the immunostimulatory activity of α‐Gal‐GSLs. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)

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A Highly Stereoselective Synthesis of α-Glucosides from 1-O-Acetyl Glucose by Use of Tin(IV) Chloride–Silver Perchlorate Catalyst System

Abstract: In the presence of a catalytic amount of tin(IV) species generated from tin(IV) chloride and silver perchlorate, 1-O-acetyl-d-glucose stereoselectively reacts with silyl alkoxides to give the corresponding α-glucosides in high yields.

Cited by 54 publications

References 15 publications

Reliable method for the synthesis of aryl β-D-glucopyranosides, using boron trifluoride–diethyl ether as catalyst

Reliable method for the synthesis of aryl β-D-glucopyranosides, using boron trifluoride–diethyl ether as catalyst

Immunomodulatory α‐Galactoglycosphingolipids: Synthesis of 2'‐Fluoro‐2'‐deoxy‐α‐galactosylceramide and an Evaluation of Its Immunostimulating Properties

Immunomodulatory α‐Galactoglycosphingolipids: Synthesis of a 2′‐O‐Methyl‐α‐Gal‐GSL and Evaluation of Its Immunostimulating Capacity

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