Eine Synthese der 6‐Desoxy‐6‐amino‐glucose

Cramer, Friedrich; Otterbach, Hans; Springmann, H.

doi:10.1002/cber.19590920221

Cited by 73 publications

(21 citation statements)

References 27 publications

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“…The greater stability of the glucoside as compared t o the xyloside is well ltnown (14). The stability towards acids of the 6-iodo-and the 6-amino glucosides has also been noted previously (15,16). In view of the postulated inductive effect of the carboxyl group, it is of interest to compare the electron affinity of the C-5 substituents with their rate coefficients.…”

Section: And Discussionsupporting

confidence: 57%

The Acid Hydrolysis of Glycosides: Ii. Effect of Substituents at C-5

Timell¹,

Enterman²,

Spencer³

et al. 1965

Can. J. Chem.

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First-order rate coefficients a t three temperatures, and energies and entropies of activation, have been determined for the acid-catalyzed hydrolysis of methyl glucopyranosides containing various substituents a t C-5 and for glycopyranosiduronic acids with different aglycones. Substitution a t C-5 increased the stability towards acids of methyl a-and P-D-glucopyranosides, but there was no correlation between either the polarity or the size of the substituent and the rates of hydrolysis. The operation of either an inductive or a coilformational effect alone was accordingly deemed unlikely.Methyl a-and 0-D-glucopyranosiduronic acids and methyl a-D-galactopyranosiduronic acid were only slightly more stable towards acids than the glycoside analogs, while benzyl 0-Dglucopyranosiduronic acid was three times more stable. T h e presence of a methyl ester group a t the carboxyl function increased the stability of the glycuronide bond. Isopropyl, n-butyl, isobutyl, and neopentyl P-D-glucopyranosiduronic acids were hydrolyzed approximately twice and cyclohexyl 0-D-glucopyranosiduronic acid five times as fast as the corresponding glucosides. This appears to be the first time that glycuronides have been found to be hydrolyzed by dilute acid a t a higher rate than their glycoside analogs.The energies and, especially, the entropies of activation were, throughout, lower for the glycuronides than for the glycosides. The difference in entropy suggests that the two classes of compounds are hydrolyzed by different mechanisms.

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Section: And Discussionsupporting

confidence: 57%

The Acid Hydrolysis of Glycosides: Ii. Effect of Substituents at C-5

Timell¹,

Enterman²,

Spencer³

et al. 1965

Can. J. Chem.

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“…In order to analyze whether the observed effects on LecB induced by cinnamide 3 are carbohydrate‐specific and to exclude simple detergent‐like denaturation of the protein, we designed its glucose‐analog 10 . The compound was synthesized in analogy to 3 : methyl α‐ d ‐glucoside ( 8 ) was transformed into the tosylate and subsequently the azide 9 was obtained after sodium azide treatment as previously reported by Cramer et al . (Scheme ).…”

Section: Resultsmentioning

confidence: 99%

“…In order to analyze whether the observed effects on LecB induced by cinnamide 3 are carbohydrate-specific and to exclude simple detergent-like denaturationo fthe protein, we designed its glucose-analog 10.T he compound was synthesized in analogy to 3:m ethyl a-d-glucoside (8)w as transformed into the tosylate and subsequently the azide 9 was obtained after sodium azide treatment as previously reported by Cramer et al [30] (Scheme 2). The azide was hydrogenolytically reduced using palladium on activated charcoal, and the resulting amine was directly coupled with cinnamic acid to yield glucocinnamide 10 in good yield (46 %o ver two steps).…”

Section: Resultsmentioning

confidence: 99%

Cinnamide Derivatives of d -Mannose as Inhibitors of the Bacterial Virulence Factor LecB from Pseudomonas aeruginosa

et al. 2015

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Pseudomonas aeruginosa is an opportunistic Gram‐negative pathogen with high antibiotic resistance. Its lectin LecB was identified as a virulence factor and is relevant in bacterial adhesion and biofilm formation. Inhibition of LecB with carbohydrate‐based ligands results in a decrease in toxicity and biofilm formation. We recently discovered two classes of potent drug‐like glycomimetic inhibitors, that is, sulfonamides and cinnamides of d‐mannose. Here, we describe the chemical synthesis and biochemical evaluation of more than 20 derivatives with increased potency compared to the unsubstituted cinnamide. The structure–activity relationship (SAR) obtained and the extended biophysical characterization allowed the experimental determination of the binding mode of these cinnamides with LecB. The established surface binding mode now allows future rational structure‐based drug design. Importantly, all glycomimetics tested showed extended receptor residence times with half‐lives in the 5–20 min range, a prerequisite for therapeutic application. Thus, the glycomimetics described here provide an excellent basis for future development of anti‐infectives against this multidrug‐resistant pathogen.

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“…These data, together with ir and 'H nmr data showing absence of benzoyl and presence of only one tosyl group besides hydroxyl, identified the product as methyl 6-0-ptolylsulfonyl-a-D-glucopyranoside (lit. (27) mp 124°C (anhydrous) and 56-58°C (hydrate)). Addition of a little hexane to the above toluene mother liquor gave a gummy deposit containing some of the same product together with the component of Rr 0.…”

Section: Methodsmentioning

confidence: 99%

The formation of branched-chain deoxypentofuranosides by ring contraction in the reductive desulfonyloxylation of hexopyranoside p-toluenesulfonates

Baer¹,

Astles²,

Chin³

et al. 1985

Can. J. Chem.

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. 63, 432 (1985). Several methyl 6-deoxy-, 6-deoxy-6-halo-, and 6-0-p-tolylsulfonylhexopyranoside 2-and 4-p-toluenesulfonates reacted readily with lithium triethylborohydride in boiling tetrahydrofuran under reductive dcsulfonyloxylation at C-2 and C-4, respectively, and with reduction at C-6 whcre applicable. The desulfonyloxylations procceded with ring contraction to furnish, in 40-60% isolated yields, new branched-chain pentofuranoside derivatives, namely, methyl 2.5-dideoxy-2-C-(hydroxymethyl)pentofuranosidcs having the a-~-xj~lo, a-D-xj~lo, and a-D-ribo configurations (from 2-tosylatcs), and methyl 3.5-dideoxy-3-C-(hydroxymethyl)pentofuranosides having the a-D-arabitzo and a-D-ribo configurations (from 4-tosylatcs). In some of the reactions, reductively desulfonyloxylated but unrearranged products were formed in addition. Methyl 4,6-0-benzylidene-2,3-di-O-p-tolylsulfonyl-a-~-gaactopyranoside reacted by partial de-0-sulfonylation and partial desulfonyloxylation, with and without ring contraction, to give methyl 3.5-0-benzyIidcne-2-deoxy-2-C-(hydroxymethyl)-a-~-/~~xo-pentofuranoside, methyl 4,6-0-benzyIidene-3-deoxy-a-~-/yxo-hexopyranosidc, and the parent 2.3-diol.

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Eine Synthese der 6‐Desoxy‐6‐amino‐glucose

Cited by 73 publications

References 27 publications

The Acid Hydrolysis of Glycosides: Ii. Effect of Substituents at C-5

The Acid Hydrolysis of Glycosides: Ii. Effect of Substituents at C-5

Cinnamide Derivatives of d -Mannose as Inhibitors of the Bacterial Virulence Factor LecB from Pseudomonas aeruginosa

The formation of branched-chain deoxypentofuranosides by ring contraction in the reductive desulfonyloxylation of hexopyranoside p-toluenesulfonates

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