Synthèse et étude R.M.N. de disaccharides et trisaccharides dans la série du l-rhamnose

Laffite, Colette; Du, Anne-Marie Nguyen Phuoc; Winternitz, F.; Wylde, Renée; Pratviel‐Sosa, Flore

doi:10.1016/s0008-6215(00)83733-7

Cited by 68 publications

(12 citation statements)

References 21 publications

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“…Twodimensional methods were used to confirm such assignments and to identify the other resonances (see below). Configurational analysis of rhamnosides and mannosides was known to be particularly difficult from the d1,2 values since both anomeric signals appears as a slightly broadened singlet with similar coupling constants (J1,z = 1.5 + 0.3 Hz) [4, 7, 81. In contrast, the chemical shifts of H-6 in thc peracetylated rhaminosidcs arc quite helpful in anomer assignments [8]. In the spectrum of the peracetylated phenolic glycolipid (Fig.…”

Section: One-dimensional Studiesmentioning

confidence: 99%

“…Similarly, it is possible to assign resonances at 4.07, 4.02 and 1.32 ppm to the 4-6 protons of sugar residue C, not previously assignable by the spindecoupling method in one-dimension NMR [4] To determine the carbohydrate substitution sites, the peracetylated phenolic glycolipid was used for 2D-COSY analysis (Fig. 4) confirm the a-configuration for both rhamnosyl residues A and 13 [8]. Therefore, the three sugar residues are linkcd by 1 + 3-linkages; in addition, the sugar residue C is necessarly a tri-0-methyl fucosyl residue.…”

Section: Two-dimensionul Chem Icul-shift Correlu Ted Spectroscopymentioning

confidence: 99%

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Scalar, dipolar‐correlated and J‐resolved 2D‐NMR spectroscopy of the specific phenolic mycoside of Mycobacterium tuberculosis

Daffé

Servin

1989

European Journal of Biochemistry

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Two-dimensional chemical shift correlated (COSY>. nuclear Overhauser (NOESYj and J-resolved spectroscopy were used to determine the complete structure of the major triglycosyl dimycocerosyl phenol phthiocerol of the tubercle bacillus (strain Canctti) without any other analytical technique. The COSY spectrum of the native glycolipid allowed the composition of the trisaccharide and the location of one methoxyl group to be determined through the assignment of the resonances of the non-anomeric methine protons. Information with respect to the configuration of the sugar residues, the pyranose structure and the linkage sites of the trisaccharide were obtained by the analysis of the COSY spectrum of the peracetylated glycolipid. The NOESY spectrum confirmed the linkage sites through the inter-residue connectivity across glycosidic linkages and allowed the determination of the sequence of the oligosaccharidc and the configuration of its sugar residues from the through-space connectivities. The J-resolved spectroscopy was used to elucidate thc structure of the glycolipid and gave additional data showing the presence of 11 non-equivalent methyl groups and allowing the recognition of two other analogucs of the phenol phthiocerol derivative in the mixture. Thus, the non-destructive 2D-NMR spectroscopy was found to be satisfactory for the analysis of mycobacterial mycosides.Most mycobacteria are endowed with large quantities of glycolipids which contain within them small oligosaccharides of sufficient antigenicity to evoke antibodies of such exquisite specificity as to allow unequivocal identification of species or subspecies [l]. This concept w-as originally formulated by Smith et al. who gave the name 'mycosides' to type-specific glycolipids of mycobacteria limited in distribution to a single species or organism 121. These specific components are of three classes: the C-mycosides (glycopeptidolipidsj, the treh, '1 1 osecontaining lipooligosaccharides, and the phenolic glycolipids To determine the primary structure of the carbohydrate moiety ol' these glycolipids, modern spectroscopic techniques, in conjunction with elaborate derivatization of substances, have been widely used. To date, no secondary structural information (conformation), which is important for understanding thc biological activities of these substances, has been publishcrl. Furthermore, proton nuclear magnetic resonance ('€1-NMK) spectroscopy, which is very suitable for providing primary and secondary structural information on glycolipids [3], yielded only fragmentary data (composition and configuration of sugar residues) in studies on mycosides.Recently, we elucidated the complete primary structure of NMR and by application of a combination of compositional analysis, mass spectrometry and chemical degradations [4, 51. The spin-decoupling method in one-dimensional NMR was found to be a powerful method for assigning the rhamnosyl ring H-1 to H-6 chemical shifts, and for analyzing the linkage sites using peracetylated glycolipids [4, 51. However, the assign...

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Section: One-dimensional Studiesmentioning

confidence: 99%

Section: Two-dimensionul Chem Icul-shift Correlu Ted Spectroscopymentioning

confidence: 99%

Scalar, dipolar‐correlated and J‐resolved 2D‐NMR spectroscopy of the specific phenolic mycoside of Mycobacterium tuberculosis

Daffé

Servin

1989

European Journal of Biochemistry

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“…The spectrum of mycoside G, but not of mycoside B (Daffk et al, 1988), was found to be superimposable on that shown in Fig. 2 (Table 2) also confirmed the a configuration of the rhamnosyl unit: 6H-5 > 4.7 p.p.m., 6H-6 < 1.2 p.p.m., (Laffite et al, 1978) and the location of the methoxyl group at position 3 (not shifted). The absolute configuration of the rhamnosyl units was determined after demethylation followed by butanolysis of the sugar constituent of both glycolipids isolated from M. ulcerans and M .…”

Section: Carbohydrate Constituent Of the Glycolipidmentioning

confidence: 99%

The phenolic mycoside of Mycobacterium ulcerans: structure and taxonomic implications

Daffé

Varnerot

Lévy-Frébault

1992

Journal of General Microbiology

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Mycobacterium ufcerans and some pathogenic mycobacterial species elaborate wax A consisting of related longchain P-diol components (phthiocerol and related compounds) esterified by multimethyl-branched fatty acids. With the exception of M. ulcerans, wax A-containing mycobacteria also synthesize glycosylated phenol phthiocerol diester and related compounds: the so-called phenolic mycosides. In a deliberate effort to characterize this latter class of compounds in M. ufcerans, 20 strains were examined. Phenolic mycosides were found in two strains. Application of chemical analyses, including one-and two-dimensional N M R spectroscopy, allowed the structural elucidation of glycolipids identified as 3-O-methyl-a-~-rhamnosyl phenol phthiocerol diphthioceranate and related compounds which correspond to mycoside G , previously characterized in M. marinum by other investigators. As phenolic mycosides are highly species-specific molecules, this finding stresses the close phylogenetic link between M. marinurn and M. ulcerans. Incidentally, a survey of the mycolate content of M. ulcerans showed that methoxymycolate could not be detected in three strains.

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“…The mother liquor was concentrated, and the residue was chromatographed in a column of silica gel (benzene-ethyl acetate, 10: I) to afford more 9 (5. (2). Deacetylation of 9 (0.3 g) with 0.1 N methanolic sodium methoxide (25 ml) gave, in a quantitative yield, 2 as a syrup, which crystallized on standing in a refrigerator, mp 103-105°C, [IXJ5° -52 0 (H 2 0).…”

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confidence: 99%

Facile Synthesis of Methyl 2-O-α-L-rhamnopyranosyl-α-L-rhamnopyranoside and Methyl 2-O-α-L-mannopyranosyl-α-L-rhamnopyranoside

Esaki

Katsumata²,

Sugiyama³

et al. 1992

Bioscience, Biotechnology, and Biochemistry

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Synthèse et étude R.M.N. de disaccharides et trisaccharides dans la série du l-rhamnose

Cited by 68 publications

References 21 publications

Scalar, dipolar‐correlated and J‐resolved 2D‐NMR spectroscopy of the specific phenolic mycoside of Mycobacterium tuberculosis

Scalar, dipolar‐correlated and J‐resolved 2D‐NMR spectroscopy of the specific phenolic mycoside of Mycobacterium tuberculosis

The phenolic mycoside of Mycobacterium ulcerans: structure and taxonomic implications

Facile Synthesis of Methyl 2-O-α-L-rhamnopyranosyl-α-L-rhamnopyranoside and Methyl 2-O-α-L-mannopyranosyl-α-L-rhamnopyranoside

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