Polymer-mediated cyclodehydration of alditols and ketohexoses

The polymer PEDOT⁺ (1 or 2) mediates a cyclodehydration reaction with alditols 3, 5, 7, 9, in hydrocarbon solvents, to give cyclic ethers 4, 6, 8, or 10, respectively, in high yield with a trivial isolation protocol. Polymers 1 or 2 also mediate the cyclodehydration of ketohexoses such as d-fructose, but not aldohexoses, to the important industrial intermediate 5-hydroxymethylfurfural (17), under milder conditions when compared to reactions mediated by mineral acids. A cascade reaction with ketohexoses is observed in toluene via cyclodehydration followed by Friedel–Crafts alkylation of the initially formed benzylic alcohol to give 16.     

Versatile syntheses of mono- or bis-allylhalothiol-carbonates of some alditol or sugar derivatives via cyclic thionocarbonates as intermediates

We describe herein an extension of the halogenation of 1,2 or 1,3-diols via a cyclic thionocarbonate functionality by reaction with an allyl halide instead of methyl iodide, which is usually used. This investigation was successfully carried out under both conventional heating and microwave solvent-free conditions with some alditol, thioanhydroalditol, and aldose derivatives.     

Orientated growth of crystalline anhydrous maltitol (4-O-alpha-D-glucopyranosyl-D-glucitol)

In the industrial crystallisation process of maltitol (C(12)H(24)O(11)), the presence of maltotriitol (C(18)H(34)O(16)) in the maltose syrup is responsible for a change of the crystal morphology. Two different crystal forms of maltitol were obtained: a prismatic one and a 'bipyramidal' one. IR and X-ray diffraction experiments (single crystal and powder) were performed to identify both crystal parameters. It is concluded that a structural polymorphism has to be ruled out. Close coincidences in some of the crystal cell parameters of maltitol and maltotriitol allow to assume the process through which maltotriitol affects the morphology of maltitol crystals.     

Synthesis of 2-deoxy-2-(4-nitroimidazol-1-yl)-D-alditols

Small molecules possessing defined configuration at centres of chirality provide a valuable chiral pool. Among different strategies applied for modification of chiral compounds, the most common is to begin with a single stereoisomer and use a synthesis that does not affect the chiral centres. The ANRORC type reaction has been applied for conversion of unprotected 2-amino-2-deoxy-D-hexopyranoses into 2-deoxy-2-(4-nitroimidazol-1-yl)-D-hexopyranoses in a reaction of some 2-aminosugars with 1,4-dinitroimidazoles. The reaction occurs with retention of configuration at C-2 of sugar ring. The products of the reaction were obtained as anomeric mixtures and separated into anomers after acetylation followed by column chromatography. 2-Deoxy-2-(4-nitroimidazol-1-yl)-D-hexopyranoses treated with sodium borohydride in methanolic solution gave the corresponding 2-deoxy-2-(4-nitroimidazol-1-yl)-D-hexitols, characterised as per-O-acetylated derivatives.     

Transport und Umsatz von Polyalkoholen bei der Hefe Rhodotorula gracilis (glutinis)

Zusammenfassung Die Polyalkohole Sorbitol, d-Mannitol, Ribitol, Xylitol, d-Arabitol, l-Arabitol und Erythritol werden von der obligat aeroben Hefe Rhodotorula gracilis über einen beweglichen Träger in der Zellmembran aufgenommen. Der Transportmechanismus ist aktiv, das erreichte Akkumulationsverhältnis ist jedoch bei allen Polyalkoholen erheblich geringer als bei Monosacchariden. Es nimmt, wie auch bei Monosacchariden, mit steigender Außenkonzentration ab, sogar auf Werte kleiner als 1.Kinetische Daten weisen darauf hin, daß das Trägersystem für Polyalkohole identisch ist mit dem für Monosaccharide, jedoch für Polyalkohole eine wesentlich geringere Affinität und maximale Geschwindigkeit aufweist. Aufgrund des hohen Affinitätsunterschiedes wird die Polyalkoholaufnahme in der Anwesenheit von Monosacchariden unterbunden.Die aufgenommenen Polyalkohole werden im Zellinneren nicht umgesetzt; eine Ausnahme stellen Ribitol und l-Arabitol dar, in deren Anwesenheit ein Abbausystem für Pentitole induziert wird.

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Transport and utilization of alditols in the yeast Rhodotorula gracilis (glutinis) I. Constitutive transport of alditols

The obligate aerobic yeast Rhodotorula gracilis was found to take up the alditols d-glucitol, d-mannitol, ribitol, xylitol, d-arabinitol, l-arabinitol and erythritol by means of a constitutive mobile membrane carrier. This uptake involved active transport, that is, it was dependent on the supply of metabolic energy, leading to the accumulation of alditols inside the cells. The accumulation ratio (intracellular concentration to extracellular concentration, S _i /S _o ) was much lower for alditols than for monosaccharides. As for monosaccharides, this ratio decreased with increasing extracellular concentration, even to values below 1.The kinetic data showed that the carrier system for alditols was identical to that for monosaccharides, though it had a much lower affinity and maximum velocity for alditols. Hence the uptake of alditols was blocked in the presence of monosaccharides.Only ribitol and l-arabinitol were catabolized following enzyme induction. The other alditols were not broken down.

     

Regioselective synthesis of alditol vicinal bis-cyclic thionocarbonates via alditol stannylene acetal complexes as a short and efficient route to alpha,omega-diiodoalditol derivatives.

The bis-cyclic thionocarbonates of alditols (pentitols and hexitols) were quickly and easily obtained from alditol stannylene complexes and phenyl chlorothionoformate (PhOC(S)Cl) in good yields. Acetylation of isolated free alditol bis-thionocarbonates and subsequent iodination using methyl iodide under pressure led to alpha,omega-diiodo derivatives of alditols in good to excellent isolated yields (67-93%).     

Fragmentation pattern of underivatised xylo-oligosaccharides and their alditol derivatives by electrospray tandem mass spectrometry

Maltopentaose and olive pulp xylo-oligosaccharides and the correspondent alditol derivatives were analysed by ESI-MS and ESI-MS/MS. The ESI-MS spectrum of maltopentaose and maltopentaose alditols showed [M+Na]⁺and [M+H]⁺ ions. ESI-MS spectrum of xylo-oligosaccharides and their alditols showed [M+Na]⁺of neutral (Xyl_3–6) and acidic (Xyl_2–3MeGlcA and Xyl_2–3GlcA) xylo-oligosaccharides. The ESI-MS/MS spectra of maltopentaose and underivatised xylo-oligosaccharides presented fragments of glycosidic cleavages attributed to B/Z and C/Y ions. On the other hand, MS/MS spectra of the correspondent alditols showed glycosidic cleavages unambiguously identified as B-type and Y-type ions. Y-type fragment ions showed higher abundance in the MS/MS spectra of the alditol derivatives when compared to the non-reduced samples. The study of the oligoxylosyl alditols fragmentation permits to distinguish fragmentation pathways that occur both from the reducing end and from the non-reducing end of the xylan chain, allowing to obtain more information about the localization of the acidic substituent along the glucuronoxylan backbone.