Cell wall lipopolysaccharide

Some examples of transformations involving carbonyl ylides are listed in Table 4.20. Entry 1 illustrates the conversion of P-acyloxy-a-diazoesters into a-acyloxyacrylates by ring fission of a cyclic carbonyl ylide [978]. This reaction has been used for the synthesis of the natural aldonic acid KDO (3-deoxy-Z)-manno-2-octulosonic acid), which is an essential component of the cell wall lipopolysaccharide of gram-negative bacteria (Figure 4.15). 

Cell-wall lipopolysaccharides of Gram-negative bacteria (Shigella strains) have also been purified by gel chromatography.122 These... 

M. A. Ghalambor and E. C. Heath, The biosynthesis of cell wall lipopolysaccharide in Escherichia coli, J. Biol. Chem. 241 3222 (1966). 

B. A. Dmitriev, Y. A. Knirel, N. K. Kochetkov, B. lann, and K. lann, Cell-wall lipopolysaccharide of the Shigella-like Escherichia coli 058. Structure of the polysaccharide chain, Eur. J. Biochem., 79 (1977) 111-115. 

Prehm, P., Stirm, S., Jann, B., Jann, K. Cell-wall lipopolysaccharide from Escherichia coli B. Eur J Biochem 56 (1975) 41-55. 

The key component of the cell wall lipopolysaccharide of Gram-negative bacteria, KDO (3-deoxy-D-manno-2-octulosonic acid), was synthesized by S.D. Burke and co-workers. One of the key transformations in the synthetic sequence was a doubie SAD of a 6-vinyldihydropyran-2-carboxylate template. This 1,4-diene was cleanly converted to a mixture of two C7 epimeric tetraols in a 20 1 ratio. The endocyclic olefin had an intrinsic preference for dihydroxyiation from the 3-face and not from the desired a-face. This stereofacial bias was impossible to override with any ligand normally used in the SAD, so later in the synthesis these two stereocenters had to be inverted in order to give the required stereochemistry at C4 and C5. 

C. G. Hellerqvist, B. Lindberg, K. Samuelsson, and R. R. Brubaker, Structural studies of the O-specific side-chains of the cell-wall lipopolysaccharide from Pasteurella pseudotuberculosis Group Ilk, Acta. Chem. Scand., 26 (1972) 1389-1393. 

Cell-wall Lipopolysaccharides of Gram-negative Bacteria. 409... 

The polysaccharide chain of the cell wall lipopolysaccharide of Escherichia coli 058 contains D-mannose, 2-acetamido-2-deoxy-D-mannose, 3-0-[(l R)-carboxyethyl)]-L-rhamnose (rhamnolytic acid), and 0-acetyl groups in the molar ratios of 2 1 1 . Structural investigations show that this polysaccharide, which contains a substituted trisaccharide repeating unit, has an identical structure (4) to that of Shigella dysenteriae type 5. 

Bacterial cell wall lipopolysaccharides of Salmonella are some of the most interesting examples of the coordinated use of sugar nucleotides involving both different sugars and different nucleotide bases. To a backbone of hexose, phosphate, and ketodeoxyoctanoate, are added in a sequential manner the sugars galactose, abequose, rhamnose, mannose, and A-acetyl-... 

Isol. from the cell wall lipopolysaccharide fraction of Pseudomonas caryophylli. Syrup. [a]o +81 (c, 1.75 in H2O). The first known naturally occurring carbocyclic sugar. 

Constit. of the cell-wall lipopolysaccharide of Salmonella newington. 

Found combined in baker s yeast, in the cell wall lipopolysaccharides of enterobacteria and the roots of Primula officinalis. A homopolymer occurs in the lipopolysaccharide of Helicobacter pylori strain D4. 

A polysaccharide isolated from a Xanthomonas species, and composed of D-glucose, D-mannose, 3-deoxy-2-octulosonic acid (KDO), and an unknown sugar component, resembles cell-wall lipopolysaccharide in containing KDO, although lipid is absent. Structural studies showed the polysaccharide to contain (1 3)- and (1 - 4)-linked hexopyranosyl residues with branching,... 

UDP-D-galactose to the terminal, non-reducing D-glucosyl residues of these oligosaccharides. The tetrasaccharide repeating unit (8) of the O-specific side-chains of the cell-wall lipopolysaccharide from E. colt 075 has been established by methylation analysis and Smith degradation. ... 

The cell-wall lipopolysaccharide of Vibrio cholerae contains neither 3-deoxy-2-octulosonic acid (as do most other enterobacterial lipopolysaccharides) nor D-galactose. ... 

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