70849-23-9Relevant academic research and scientific papers
Successive C1-C2 bond cleavage: The mechanism of vanadium(v)-catalyzed aerobic oxidation of d-glucose to formic acid in aqueous solution
Niu, Muge,Hou, Yucui,Wu, Weize,Ren, Shuhang,Yang, Ru
, p. 17942 - 17951 (2018/07/14)
Vanadium(v)-catalyzed aerobic oxidation in aqueous solution shows high selectivity in the field of C-C bond cleavage of carbohydrates for chemicals with less carbon atoms. However, the pathway of C-C bond cleavage from carbohydrates and the conversion mechanism are unclear. In this work, we studied the pathway and the mechanism of d-glucose oxidation to formic acid (FA) in NaVO3-H2SO4 aqueous solution using isotope-labeled glucoses as substrates. d-Glucose is first transformed to FA and d-arabinose via C1-C2 bond cleavage. d-Arabinose undergoes similar C1-C2 bond cleavage to form FA and the corresponding d-erythrose, which can be further degraded by C1-C2 bond cleavage. Dimerization and aldol condensation between carbohydrates can also proceed to make the reaction a much more complicated mixture. However, the fundamental reaction, C1-C2 bond cleavage, can drive all the intermediates to form the common product FA. Based on the detected intermediates, isotope-labelling experiments, the kinetic isotope effect study and kinetic analysis, this mechanism is proposed. d-Glucose first reacts with a vanadium(v) species to form a five-membered-ring complex. Then, electron transfer occurs and the C1-C2 bond weakens, followed by C1-C2 bond cleavage (with no C-H bond cleavage), to generate the H3COO-vanadium(iv) complex and d-arabinose. FA is generated from H3COO that is oxidized by another vanadium(v) species. The reduced vanadium species is oxidized by O2 to regenerate to its oxidation state. This finding will provide a deeper insight into the process of C-C bond cleavage of carbohydrates for chemical synthesis and provide guidance for screening and synthesizing new highly-efficient catalyst systems for FA production.
Phosphate-catalyzed degradation of d-glucosone in aqueous solution is accompanied by C1-C2 transposition
Zhang, Wenhui,Serianni, Anthony S.
, p. 11511 - 11524 (2012/08/28)
Pathways in the degradation of the C6 1,2-dicarbonyl sugar (osone) d-glucosone 2 (d-arabino-hexos-2-ulose) in aqueous phosphate buffer at pH 7.5 and 37 °C have been investigated by 13C and 1H NMR spectroscopy with the use of singly and doubly 13C-labeled isotopomers of 2. Unlike its 3-deoxy analogue, 3-deoxy-d-glucosone (3-deoxy-d-erythro-hexos-2-ulose) (1), 2 does not degrade via a 1,2-hydrogen shift mechanism but instead initially undergoes C1-C2 bond cleavage to yield d-ribulose 3 and formate. The latter bond cleavage occurs via a 1,3-dicarbonyl intermediate initially produced by enolization at C3 of 2. However, a careful monitoring of the fates of the sketetal carbons of 2 during its conversion to 3 revealed unexpectedly that C1-C2 bond cleavage is accompanied by C1-C2 transposition in about 1 out of every 10 transformations. Furthermore, the degradation of 2 is catalyzed by inorganic phosphate (Pi), and by the Pi-surrogate, arsenate. C1-C2 transposition was also observed during the degradation of the C5 osone, d-xylosone (d-threo-pentose-2- ulose), showing that this transposition may be a common feature in the breakdown of 1,2-dicarbonyl sugars bearing an hydroxyl group at C3. Mechanisms involving the reversible formation of phosphate adducts to 2 are proposed to explain the mode of Pi catalysis and the C1-C2 transposition. These findings suggest that the breakdown of 2 in vivo is probably catalyzed by Pi and likely involves C1-C2 transposition.
Reaction pathways of glucose oxidation by ozone under acidic conditions
Marcq, Olivier,Barbe, Jean-Michel,Trichet, Alain,Guilard, Roger
experimental part, p. 1303 - 1310 (2009/12/01)
The ozonation of d-glucose-1-13C, 2-13C, and 6-13C was carried out at pH 2.5 in a semi-batch reactor at room temperature. The products present in the liquid phase were analyzed by GC-MS, HPAEC-PAD, and 13C NMR s
The economical synthesis of [2'-(13)C, 1,3-(15)N2]uridine; preliminary conformational studies by solid state NMR.
Patching, Simon G,Middleton, David A,Henderson, Peter J F,Herbert, Richard B
, p. 2057 - 2062 (2007/10/03)
The synthesis of [2'-(13)C, 1,3-(15)N2]uridine 11 was achieved as follows. An epimeric mixture of D-[1-(13)C]ribose 3 and D-[1-(13)C]arabinose 4 was obtained in excellent yield by condensation of K13CN with D-erythrose 2 using a modification of the Kiliani-Fischer synthesis. Efficient separation of the two aldose epimers was pivotally achieved by a novel ion-exchange (Sm3+) chromatography method. D-[2-(13)C]Ribose 5 was obtained from D-[1-(13)C]arabinose 4 using a Ni(II) diamine complex (nickel chloride plus TEMED). Combination of these procedures in a general cycling manner can lead to the very efficient preparation of specifically labelled 13C-monosaccharides of particular chirality. 15N-labelling was introduced in the preparation of [2'-(13)C, 1,3-(15)N2]uridine 11 via [15N2]urea. Cross polarisation magic angle spinning (CP-MAS) solid-state NMR experiments using rotational echo double resonance (REDOR) were carried out on crystals of the labelled uridine to show that the inter-atomic distance between C-2' and N-1 is closely similar to that calculated from X-ray crystallographic data. The REDOR method will be used now to determine the conformation of bound substrates in the bacterial nucleoside transporters NupC and NupG.
SYNTHESIS OF L-(4-2H)ERYTHROSE, L-(1-13C, 5-2H)ARABINOSE AND L-(2-13C, 5-2H)ARABINOSE AND IDENTIFICATION OF THE INTERMEDIATES BY 2H AND 13C-N.M.R. SPECTROSCOPY
Han, Chung H.,Sillerud, Laurel O.
, p. 247 - 264 (2007/10/02)
L-(1-13C, 5-2H)Arabinose (6D) and L-(2-13C, 5-2H)arabinose (8D) have been synthesized by degradation of 2,3-O-isopropylidene-β-L-rhamnofuranose (2) to L-(4-2H)erythrose (5β, 5αD), with subsequent chain elongation to 6D plus L-(1-13C, 5-2H)ribose (7D), the latter being converted into 8D.Intermediates were identified by complete assignment of the 13C chemical shifts employing carbon-carbon and carbon-deuterium coupling constants, deuteration shifts, differential isotope-shifts, and deuterium spectra.The anomeric carbon atoms of 2 and 2,3-O-isopropylidene-L-(1-2H)erythrose (4D) gave only single 13C resonances, suggesting that these two compounds exists in only one major anomeric configuration, clarifying previously reported work.The synthesis of 2,3-O-isopropylidene-L-(1-2H)rhamnitol (3D) facilitated the assignment of the signals in the 13C spectra of the nondeuterated analog.Specific deuterium-enrichment and the observed carbon-deuterium coupling (1JC,D ca. 22 Hz) not only served to identify the deuterated carbon atom unambiguously in 3 but also permitted assignment of closely spaced resonances.The deuterium spectrum of 2,3-O-isopropylidene-L-(4-2H)erythrofuranose (4D) showed only a single resonance, indicating preponderance of one anomer, in accord with the observation of a single C-1 resonance in the 13C spectrum.
Paramolybdate anion-exchange resin, an improved catalyst for the C-1-C-2 rearrangement and 2-epimerization of aldoses.
Clark Jr.,Hayes,Barker
, p. 263 - 270 (2007/10/02)
Aqueous solutions of molybdate at 90 degrees bring about the inversion of the C-1-C-2 fragment of aldoses having four or more carbon atoms, generating thermodynamically equilibrated mixtures of the starting aldose and its 2-epimer. In some cases, notably with the aldopentoses, substantial proportions of the 3-epimers are produced, as well as 2-epimers that have not undergone inversion of the C-1-C-2 fragment. These side-reactions can be controlled by using the paramolybdate form of an anion-exchange resin (AG MP-1) together with the formate form of the same resin. The latter acts to scavenge unbound molybdate and paramolybdate anions that appear to be responsible for the side reactions.
