Configuration of the acetal carbon atom of pyruvic acid acetals in some bacterial polysaccharides

1980 ◽  
Vol 78 (1) ◽  
pp. 127-132 ◽  
Author(s):  
Per J. Garegg ◽  
Per-Erik Jansson ◽  
Bengt Lindberg ◽  
Frank Lindh ◽  
Jörgen Lönngren ◽  
...  
1989 ◽  
Vol 67 (6) ◽  
pp. 998-1009 ◽  
Author(s):  
Gunnar Grue-Sørensen ◽  
Ian D. Spenser

It is shown by 13C nuclear magnetic resonance spectroscopy that the labelled C2 fragment of [2,3-13C2]pyruvic acid is transferred intact into the C-methyl group and the adjacent carbon atom of the Ephedra alkaloids, norephedrine, ephedrine, norpseudoephedrine, and pseudoephedrine, in growing plants of Ephedragerardiana. This finding serves to identify pyruvate as the elusive precursor of the aliphatic C2 terminus of the skeleton of the alkaloids. In earlier experiments with C-labelled substrates, label from [3-14C]pyruvic acid was incorporated mainly, but not exclusively, into the C-methyl group of ephedrine, and label from [2-14C]pyruvate was incorporated similarly into the carbon atom adjacent to the C-methyl group. A C6–C1 unit related to benzaldehyde or benzoic acid has long been known to generate the benzylic fragment of the carbon skeleton of the Ephedra alkaloids. It is likely that the carbon skeleton of ephedrine is generated from pyruvate and either benzaldehyde or benzoic acid, by a reaction analogous to the formation of acetoin or diacetyl from pyruvate and acetaldehyde or acetic acid, respectively. Keywords: biosynthesis of ephedrine, Ephedra alkaloids, 13C NMR spectra, ephedrine, biosynthesis of pyruvic acid, incorporation into ephedrine13C NMR spectra.


1999 ◽  
Vol 77 (11) ◽  
pp. 1707-1715 ◽  
Author(s):  
Peter J Heard ◽  
Alex D Bain ◽  
Paul Hazendonk

Tricarbonylrhenium(I) halide complexes of the nonracemic chiral ligand 2-[(4R,5R)-dimethyl-1,3-dioxan-2-yl]pyridine (L), namely fac-[ReX(CO)3L] (X = Cl, Br, or I), have been prepared and their latent fluxionality studied by dynamic NMR techniques in the slow and intermediate exchange regimes. In solution, these complexes give rise to four diastereoisomers, depending on the configuration at the metal and at the acetal-carbon atom, respectively; the relative populations are in the order SR > RR >>; RS > SS. At moderate temperatures, a reversible "acetal ring flip" leads to formal inversion of configuration at the acetal-carbon atom; the free energies of activation are in the range 84-88 kJ mol-1 at 298 K. Above ca. 370 K, reversible ligand dissociation also occurs, leading to an exchange of all four diastereoisomers on the NMR chemical shift time-scale.Key words: dynamic NMR, fluxionality, tricarbonylrhenium(I) complexes, chiral acetal ligands.


Author(s):  
M.J. Witcomb ◽  
M.A. O'Keefe ◽  
CJ. Echer ◽  
C. Nelson ◽  
J.H. Turner ◽  
...  

Under normal circumstances, Pt dissolves only a very small amount of interstitial carbon in solid solution. Even so, an appropriate quench/age treatment leads to the formation of stable Pt2C {100} plate precipitates. Excess (quenched-in) vacancies play a critical role in the process by accommodating the volume and structural changes that accompany the transformation. This alloy system exhibits other interesting properties. Due to a large vacancy/carbon atom binding energy, Pt can absorb excess carbon at high temperatures in a carburizing atmosphere. In regions rich in carbon and vacancies, another carbide phase, Pt7C which undergoes an order-disorder reaction was formed. The present study of Pt carburized at 1160°C and aged at 515°C shows that other carbides in the PtxC series can be produced.


1970 ◽  
Vol 24 (03/04) ◽  
pp. 432-437 ◽  
Author(s):  
S Cronberg ◽  
J. P Caen

SummaryReports on platelet aggregation after addition of calcium or magnesium to EDTA- PRP or platelet suspensions were confirmed. An aggregating principle was found in the EDTA-plasma and the supernatant of the platelet suspensions. Aggregation by magnesium in a platelet suspension was inhibited by adenosine and phosphoenol- pyruvic acid and pyruvate kinase, which suggested that the active principle was identical with ADP. Degradation of ADP in EDTA plasma was blocked.It thus appears that aggregation induced by calcium or magnesium in EDTA-PRP and platelet suspension was due to accumulation of spontaneously liberated ADP, which was not degraded.


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