Synthesis and surface-active properties of some alkyl 2-amino-2-deoxy-β-d-glucopyranosides

Boullanger, Paul; Chevalier, Yves; Croizier, M.‐C.; Lafont, Dominique; Sancho, Marie-Rose

doi:10.1016/0008-6215(95)00229-1

Cited by 23 publications

(11 citation statements)

References 16 publications

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“…The anomeric proton at δ 5.16 together with six proton signals at δ 4.00–4.57 suggested a glycosyl moiety similar to 1 . Among these carbinol methine and methylene protons, the signal at δ 4.41 (H-2’) correlated with an upfield-shifted carbon signal at δ 57.9 (C-2’) in the HSQC spectrum, indicating that this glycosyl moiety was an aminoglucoside 13,14. In addition, an acetyl function [ 1 H (δ 2.13) and 13 C (δ 170.7 and 24.0)] was identified.…”

Section: Resultsmentioning

confidence: 96%

Structure and biological evaluation of novel cytotoxic sterol glycosides from the marine red alga Peyssonnelia sp.

Lin¹,

Engel²,

Smith³

et al. 2010

Bioorganic & Medicinal Chemistry

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Bioactivity-guided fractionation of the extract from a Fijian red alga Peyssonnelia sp. led to the isolation of two novel sterol glycosides 19-O-β-D-glucopyranosyl-19-hydroxy-cholest-4-en-3-one (1) and 19-O-β-D-N-acetyl-2-aminoglucopyranosyl-19-hydroxy-cholest-4-en-3-one (2), and two known alkaloids indole-3-carboxaldehyde (3) and 3-(hydroxyacetyl)indole (4). Their structures were characterized by 1D and 2D NMR and mass spectral analysis. The sterol glycosides inhibited cancer cell growth with mean IC 50 values (for 11 human cancer cell lines) of 1.63 and 1.41 µM for 1 and 2, respectively. The most sensitive cancer cell lines were MDA-MB-468 (breast) and A549 (lung), with IC 50 s in of 0.71-0.97 µM for 1 and 2. Modification of the sterol glycoside structures revealed that the α,β-unsaturated ketone at C-3 and oxygenation at C-19 of 1 and 2 are crucial for anticancer activity, whereas the glucosidic group was not essential but contributed to enhanced activity against the most sensitive cell lines.

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Section: Resultsmentioning

confidence: 96%

Structure and biological evaluation of novel cytotoxic sterol glycosides from the marine red alga Peyssonnelia sp.

Lin¹,

Engel²,

Smith³

et al. 2010

Bioorganic & Medicinal Chemistry

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“…5-Fluoro-glucosamine 1-phosphate, UDP-(5-F)-GlcNAc, and octyl 5-fluoro-2-deoxy-2-acetamido-β-D-glucopyranoside ((5-F)-GlcNAc β-octyl glycoside) were synthesized as previously described (13). GlcNAc β-octyl glycoside was synthesized as described in the literature (22). Pyridinium acetate solutions were prepared by adding the requisite amount of acetic acid followed by addition of pyridine to pH 4.5 and dilution with water to provide the desired concentration.…”

Section: Experimental Procedures Materialsmentioning

confidence: 99%

Glycosyltransferase Mechanisms: Impact of a 5-Fluoro Substituent in Acceptor and Donor Substrates on Catalysis

et al. 2007

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In glycosyltransferase-catalyzed reactions a new carbohydrate-carbohydrate bond is formed between a carbohydrate acceptor and the carbohydrate moiety of either a sugar nucleotide or lipid-linked saccharide donor. It is currently believed that most glycosyltransferase-catalyzed reactions occur via an electrophilic activation mechanism with the formation of an oxocarbenium ion-like transition state, a hypothesis that makes clear predictions regarding the charge development on the donor (strong positive charge) and acceptor (minimal negative charge) substrates. To better understand the mechanism of these enzyme-catalyzed reactions, we have introduced a strongly electronwithdrawing group (fluorine) at C-5 of both donor and acceptor substrates in order to explore its effect on catalysis. In particular, we have investigated the effects of the 5-fluoro analogs on the kinetics of two glycosyltransferase-catalyzed reactions mediated by UDP-GlcNAc:GlcNAc-P-P-Dol N-acetylglucosaminyltransferase (chitobiosyl-P-P-lipid synthase, CLS) and β-Nacetylglucosaminyl-β-1,4 galactosyltransferase (GalT). The 5-fluoro group has a marked effect on catalysis when inserted into the UDP-GlcNAc donor, with the UDP(5-F)-GlcNAc serving as a competitive inhibitor of CLS rather than a substrate. The (5-F)-GlcNAc β-octyl glycoside acceptor; however, is an excellent substrate for GalT. Both of these results support a weakly associative transition state for glycosyltransferase-catalyzed reactions that proceed with inversion of configuration.Glycosyltransferases are involved in a wide variety of biological processes ranging from the processing of N-linked glycan structures (1) to signal transduction (2) to bacterial cell wall (3) and natural product synthesis (4). A thorough understanding of these enzyme-catalyzed reactions will be important for the design of molecular therapeutics targeting these enzymes. Based on sequence homology, glycosyltransferases have been classified into an expanding list of families (5) (89 as of April 2007; available at http://afmb.cnrs-mrs.fr/CAZY. Despite this sequence diversity, glycosyltransferases can be classified into three superfamilies based on current crystal structures (6). Although there are likely to be some subtle differences between the superfamilies, the mechanisms of glycosyltransferase-catalyzed reactions fall into two categories: retaining, where the product glycoside has the same stereochemistry as the activated † This research was supported in part by the Vahlteich Research Fund administered by the College of Pharmacy, University of Michigan (JKC) and by NIH grant GM36065 (CJW).*To whom correspondence should be addressed: Phone: 734-936-2843. FAX: 734-647-4865. E-mail: jkcoward@umich.edu NIH-PA Author ManuscriptNIH-PA Author Manuscript NIH-PA Author Manuscript leaving group, and inverting, where the reaction proceeds with inversion of stereochemistry at C-1.A number of studies using substrate analogs (7-9) have suggested that inverting glycosyltransferase-catalyzed reactions, like those of g...

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“…illustrates some recently synthesized 2-amino glucose-based ionic and nonionic surfactants (9)(10)(11)(12)(13)(14). Some of the cationic surfactants shown in Figure 1 have bacteriostatic properties and are more biodegradable than currently employed quaternary ammonium compounds, e.g., cetyltrimethylammonium halides (15)(16)(17).…”

mentioning

confidence: 99%

Sugar‐based cationic surfactants: Synthesis and aggregation of methyl 2‐acylamido‐6‐trimethylammonio‐2,6‐dideoxy‐d‐glucopyranoside chlorides

Bazito

Seoud

2001

J Surfact & Detergents

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The synthesis of the sugar-based cationic surfactants methyl 2-acylamido-6-trimethylammonio-2,6-dideoxy-Dglucopyranoside chlorides is reported here. Aggregation of these surfactants (predominantly α anomers) in water was studied at 25°C by conductivity measurements. Increasing the chain length of the amido group R decreased the critical micelle concentration (CMC) and the degree of counter-ion dissociation. The dependence of the Gibbs' free energy of micellization and CMC on the length of R is similar to that observed for other ionic surfactants. The free energy of transfer of the head group, i.e., cationic amino sugar moiety, from water to the micelle is more negative than that of other ionic surfactants, including sodium methyl 2-acylamido-2-deoxy-6-O-sulfo-D-glucopyranosides, probably due to a combination of a micellar "medium" effect and intermolecular H-bonding in the micellar pseudophase.The impetus for the intense interest in studying ionic and nonionic sugar-based surfactants stems from the fact that they are biodegradable, very mild to the skin, and are derived from renewable sources (1). Currently, these surfactants are present in commercial powder and liquid formulations (2,3) and are employed in nondenaturing extraction and purification of membrane proteins (4,5) and in increasing the colloidal stability of liposomes (6).The compound 2-amino-2-deoxy-D-glucopyranose (hereafter called 2-amino glucose) is widely present in nature, e.g., as the building block of chitin, the second-most abundant natural polymer after cellulose (7). It is also a main component of peptidoglycan, the backbone of the cell wall of numerous bacteria. Much attention has been focused on sugar-based surfactants, although amino sugars carry two different functional groups, namely, NH 2 and OH, that could, in principle, be derivatized (8). Figure 1 illustrates some recently synthesized 2-amino glucose-based ionic and nonionic surfactants (9-14). Some of the cationic surfactants shown in Figure 1 have bacteriostatic properties and are more biodegradable than currently employed quaternary ammonium compounds, e.g., cetyltrimethylammonium halides (15-17). As can be seen from Figure 1, the positive charge is present in the ring 2-position, namely, in the form of NH 3 + or N(CH 3 ) 3 + . To our knowledge, there has been no report on methyl 2-acylamido-6-trimethylammonio-2,6-dideoxy-D-glucopyranoside halides. We decided therefore to synthesize these surfactants (as chlorides) and to study effects of increasing the length of their hydrophobic moiety (acyl group = octanoyl, dodecanoyl, and hexadecanoyl) on aggregate formation in water. We were also interested in comparing their micellar properties with those of recently synthesized 2-amino glucose-based anionic surfactants that carry the same acyl groups, namely, sodium methyl 2-acylamido-2-deoxy-6-Osulfo-D-glucopyranosides (18). EXPERIMENTAL PROCEDURESMaterials. The solvents and reagents were purchased from Aldrich (Milwaukee, WI) or Merck (Darmstadt, Germany) and were purified by standard p...

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Synthesis and surface-active properties of some alkyl 2-amino-2-deoxy-β-d-glucopyranosides

Cited by 23 publications

References 16 publications

Structure and biological evaluation of novel cytotoxic sterol glycosides from the marine red alga Peyssonnelia sp.

Structure and biological evaluation of novel cytotoxic sterol glycosides from the marine red alga Peyssonnelia sp.

Glycosyltransferase Mechanisms: Impact of a 5-Fluoro Substituent in Acceptor and Donor Substrates on Catalysis

Sugar‐based cationic surfactants: Synthesis and aggregation of methyl 2‐acylamido‐6‐trimethylammonio‐2,6‐dideoxy‐d‐glucopyranoside chlorides

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