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.

From biomass to a renewable LixC6O6 organic electrode for sustainable Li-ion batteries.

Li-ion batteries presently operate on inorganic insertion compounds. The abundance and materials life-cycle costs of such batteries may present issues in the long term with foreseeable large-scale applications. To address the issue of sustainability of electrode materials, a radically different approach from the conventional route has been adopted to develop new organic electrode materials.

A concise synthesis of 5-amino-5-deoxyaldonic acids as monomers for the preparation of nylon 5.

Saponification of 5-azido-5-deoxy-D-pentonolactones (ribo-, arabino-, xylo-) with NaOH gave the corresponding 5-azido-5-deoxyaldonic acids sodium salts which, after regeneration of the acid form followed by catalytic reduction, led to the target compounds in 98% overall yields.

Direct syntheses of S-alkylthio-D-galactono-, D-mannono-1,4-lactones, S-alkylthio-L-galactitols and D-mannitols displaying amphiphilic and mesophasic properties.

Alkylthio-L-galactitols and D-mannitols were obtained in good yields (70-81%) by reduction, with NaBH4, of the corresponding 6-S-alkyl-6-thio-D-hexono-1,4-lactones.

An efficient way to 1,7-enynes and ethyl 8-yn-2-enoates from aldohexoses and to polyhydroxylated 1-vinylcyclohexenes.

In this paper, we report the synthesis of carbohydrate-derived 1,7-enynes and subsequent metathesis to yield polyhydroxylated 1-vinylcyclohexenes. For example, we converted D-glucose 2 to the (6,7)-dideoxy-D-gluco-hept-6-ene-pyranose 7, which led to the desired 1,7-enyne 16. The ring-closing metathesis of this 1,7-enyne 16 with the second generation Grubbs catalyst, under Mori's conditions, gave the corresponding polyhydroxylated 1-vinylcyclohexene 25 in 76% yield.

Synthesis and amphiphilic properties of S-alkylthiopentonolactones and their pentitol derivatives.

The amphiphilic properties of S-alkylthiopentono-1,4-lactones (D-ribono-, D-arabinono-, D-xylono-) and corresponding pentitol derivatives with the general formula Su-SR (R=CnH2n+1) are studied. It was shown that CMC, surface area, CPP, and pC20 are influenced by the following structural parameters: alkyl chain length, the number of free hydroxyls, cyclic or acyclic Su structure, and alditol configuration.

Efficient synthesis of 5-thio-D-arabinopyranose and 5-thio-D-xylopyranose from the corresponding D-pentono-1,4-lactones.

5-Thio-D-arabinopyranose (5) and 5-thio-D-xylopyranose (10) were synthesized from the corresponding D-pentono-1,4-lactones. After regioselective bromination at C-5, transformation into 5-S-acetyl-5-thio derivatives, reduction into lactols and deprotection afforded the title compounds in 49 and 42% overall yield, respectively.

Synthesis and characterization of mannosyl mimetic derivatives based on a beta-cyclodextrin core.

The synthesis of branched beta-cyclodextrins substituted with mannosyl mimetic derivatives at one primary hydroxy group is described. It was shown that the self-inclusion phenomenon observed for the target compounds in water did not preclude the inclusion properties of the cyclodextrin moiety.

Peracetylated 1,6-dibromo-D-glucitol as efficient precursor of 1,6-diiodo and some mono-, disubstituted and heterocyclic D-glucitol derivatives.

2,3,4,5-Tetra-O-acetyl-1,6-dibromo-1,6-dideoxy-D-glucitol (1a) obtained from D-glucitol was easily transformed into the 1,6-diiodo derivative in excellent yield (97%) by reaction with an excess of sodium iodide in refluxing butanone in 2 h. When the reaction time was prolonged to 24 h and the crude product was acetylated, 1,2,3,4,5-penta-O-acetyl-6-deoxy-6-iodo-D-glucitol and D-glucitol hexaacetate were isolated in 50 and 26% yields, respectively. The monodehalogenation then took place regioselectively at C-1.

An improved synthesis of 5-thio-D-ribose from D-ribono-1,4-lactone.

5-Thio-D-ribopyranose was synthesized from D-ribono-1,4-lactone (1) by two approaches: (i) 5-bromo-5-deoxy-D-ribono-1,4-lactone (2) was successively transformed into 5-bromo-5-deoxy, 5-S-acetyl-5-thio or 5-thiocyanato-D-ribofuranose derivatives; appropriate treatment then lead to 5-thio-D-ribopyranose (7) in 46-48% overall yield and; (ii) 2 was transformed into the 5-S-acetyl-5-thio-D-ribono-1,4-lactone derivative (11). Reduction and deprotection of 11 afforded 5-thio-D-ribopyranose (7) in 57% overall yield.

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%).

Efficient syntheses of 1-S-alkyl-1-thio-L-ribitols, D-lyxitols and L-xylitols from D-pentono-1,4-lactones.

The thioalkylation of unprotected 5-bromo-5-deoxy-D-ribono, D-arabinono, and D-xylono-1,4-lactone was performed with the alkylthiol-sodium hydride reagent. The corresponding 5-S-alkyl-5-thio-D-pentono-1,4-lactones were isolated in good yields (82-95%). Reduction with NaBH(4) of these derivatives gave the 1-S-alkyl-1-thio-L-ribitols, D-lyxitols and L-xylitols in 85-96% yields.

Three step synthesis of aminocyclohexitols from unprotected aldoses.

We report an efficient three step synthesis of aminocyclohexitols from aldohexoses without the use of protecting groups. Unprotected aldohexoses are selectively halogenated at the primary carbon, the aldehyde function is then transformed into an oxime ether and finally free radical cyclization of these precursors gives aminocyclohexitols.