- Biosynthesis of Natural Products with a P-C Bond, I. - Incorporation of D-Glucose into (2-Aminoethyl)phosphonic Acid in Tetrahymena thermophila
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The phosphate-phosphonate rearrangement is tested as a model reaction for the biosynthesis of the P-C bond as alternative to the rearrangement of phosphoenolpyruvate.D-glucose was prepared and added to the growth medium of Tetrahymena thermophila. (2-Aminoethyl)phosphonic acid (AEP) (1) was isolated from the wet cell mass by hydrolysis with 6N HCl and ion exchange chromatography and was derivatized to the crystalline 4-bromobenzamide 26.The amount of -AEP in admixture with unlabeled AEP was up to 43percent, which is not in agreement with an enzymic phosphate-phosphonate rearrangement of dihydroxyacetone phosphate, for which monodeutereated AEP would be expected.For comparison -AEP (31) was prepared starting from 2-amino-ethanol.
- Hammerschmidt, Friedrich
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p. 531 - 536
(2007/10/02)
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- NUCLEAR MAGNETIC RESONANCE STUDIES OF D-ERYTHROSE 4-PHOSPHATE IN AQUEOUS SOLUTION. STRUCTURES OF THE MAJOR CONTRIBUTING MONOMERIC AND DIMERIC FORMS
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N.m.r. studies show that a concentrated (ca. 1.0 M ) aqueous solution of D-erythrose 4-phosphate is composed of an equilibrium mixture of the monomeric aldehyde and hydrated aldehyde forms, which interconvert rapidly, together with a major contribution from three dimeric forms.In dilute solutions (ca. 0.04 M ), the hydrated monomer is predominant and dimeric forms are not detectable at this concentration.The chemical structures and stereochemistry of the three dimers have been elucidated by (1)H- and (13)C n.m.r. spectroscopy of D-erythrose 4-phosphate and its (4,4-2H2) and (3,4,4'-2H3) derivatives, aided by the use of the model compounds, glycolaldehyde, D-glyceraldehyde, and DL-glyceraldehyde 3-phosphate, which also form dimers in concenrated aqueous solution.In some cases, the tert-butyldimethylsilyl derivatives of the model dimeric compounds were prepared and isolated.The two major dimers of D-erythrose 4-phosphate, I and II are asymmetrically substituted 1,3-dioxane and 1,3-dioxolane stuctures, respectively, and dimer III is the α anomer of dimer I.
- Duke, Colin C.,MacLeod, John K.,Williams, John F.
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