Dérivés du C-méthyl-3-xylofurannose

3-C-Methylxylofuranose Derivatives 3′-C-methyladenosine has been known for almost ten years whereas its 3′-epimer is still to be prepared, because of the difficulty of synthesizing the 3-C-methylxylo-furanose. In this communication, the synthesis of 1,2-O-isoproypylidene acetal 9 and its derivatives is described. Vicinal dihydroxylation of 5-O-benzoyl-3-deoxy-1,2-O-isopryopylidene-3-C-methylidene-α-D -erythro-pentofuranose ( 6 ) led to the branchedchain sugar derivative 7 which was selectively tosylated to 8 whose reduction gave 9 . These reactions, as well as the derivatizations of 7 , 8 and 9 , took place with good to excellent yields.     

C-nucleosides aminoisoxazoliques. Communication préliminaire

Aminoisoxazoles C-nucleosides Upon treatment with bromocyanomethylenetriphenylphosphorane, a series of aldehydosugar derivatives gave in good to excellent yields the corresponding terminal gem-bromocyanoenoses 3 , 7–10 and 16 . Reacted with hydroxylamine, these unsaturated sugars led to the expected [3] 5-amino-3-glycosylisoxazoles 4 , 11 , 12 and 17 , whereas using hydroxyurea as a binucleophile they gave the corresponding 3-amino-5-glycosylisoxazoles 13 and 14 as previously described in other series [3]. The major interest of these compounds rests in their being close analogs (or enantiomers of analogs) of important biological compounds as f.e. AICAR.     

Préparation de phosphonates de sucres ramifiés par addition nucléophile conjuguée. Communication préliminaire

Preparation of unsaturated sugars phosphonates using nucleophilic conjugate addition Different types of phosphorus nucleophiles underwent conjugate addition reaction with one of the branched-chain sugars 4, 5 or 11 the addition taking place either on the endo or the exo face of the furanose ring (or on both faces in the case of 11 ). The configuration at C(3) of these new phosphorus-bearing types of sugars as well as the configuration at the phosphorus atom of the cyclic phosphinates 9 and 10 was established by NMR. (³J_P,H–C(2), ³J_P,C(1)). Small amounts (7%) of the spiro enol phosphonate 16 were formed when 11 reacted with trimethyl phosphite.     

Utilisation d'ylides du phosphore en chimie des sucres. XVIII Synthèse de furannoses à insaturation conjuguée. Communication préliminaire

Several sugars with conjugated unsaturation (dienes or α, β-unsaturated carbonyl compounds) have been synthesised by use of Wittig reactions. Keto-sugars bearing a carbonyl group α to a furanose ring are prone to undergo an elimination leading to conjugated unsaturated systems. This constitutes a novel kind of side-reaction in the application of Wittig reactions to carbonyl sugars. The synthesis of a new kind of acetylenic sugar is also described.     

Dárivás C-glycosyliques. IX. Syntháse de spiro-Δ2-isoxazolines et de spiro-Δ1-pyrazolines à partir du dásoxy-3-di-O-isopropylidène 1, 2: 5, 6-máthylène-3-α-D-ribo-hexofurannose. Communication práliminaire

Treatment of 3-deoxy-1, 2:5, 6-di-O-isopropylidène-3C-méthylene-α-D -ribo-hexofuranose with aromatic nitrile oxides led to spiro-Δ₂-isoxazolines, whereas a Δ₁-pyrazoline was obtained by reacting the same C-methylenic sugar with diazomethane. Properties of these compounds, a new class of carbohydrates, and 5, 6-di-O-acetyl derivatives thereof are described.     

Etude par spectrométrie de masse des O-isopropylidène-1,2-thréo- et -érythro-furannoses et des quatre désoxy-5-O-isopropylidène-1,2-pentofurannoses

The mass spectra of the O-isopropylidene derivatives of threo- and erythro-furanose and those of the four C(4) methylated stereoisomers have been studied. Fragmentation modes based upon deuterium labelling, metastable peaks and high-resolution measurements are proposed. Each stereoisomer can be characterized by its low-resolution mass spectrum.     

Equilibres conformationnels de glucides au niveau de liaisons σ sp2-sp3 C-C. III Dérivés d'oximes d'aldéhydo-sucres utilisation de tris-dipivaloylméthanato-europium

A series of sugar oximes and O-methyloximes of the general formula RCH?NOR′ (R′ ? H, CH₃) have been studied by PMR. spectroscopy. These compounds exist in solution as a mixture of the syn and anti isomers. The conformational equilibrium of the syn isomers seems to consist exclusively of the eclipsed rotamers, whereas for the anti isomers there appears to be a significant contribution from bisecting rotamers. Using tris-dipivaloylmethanato-europium it is found that the α proton of the anti oximes is much more deshielded than the corresponding proton of the syn isomers, which means that the downfield shift of a particular proton does not depend exclusively on its distance from the oxygen of the oxyimino group.     

C-Glycosides,IV. Mise en évidence d'un mécanisme concurrent de la cyclo-addition dipolaire-1,3 concertée lors de la réaction d'une azométhine-imine avec un dipolarophile acétylénique. Communication préliminaire

The reaction of a glycosyl-azomethine imine with an acetylenic dipolarophile in the usual conditions for 1, 3-dipolar cycloaddition led to an α-ethynyl-hydrazone beside the ‘normal’ product of the reaction, i.e. the corresponding pyrazole. Deuteration experiments indicated that the two products are formed by two concurrent independent pathways. It is supposed that the slow step in the formation of the α-acetylenic hydrazone is the ionization of the alcyne whose conjugated base reacts rapidly with the 1, 3-dipole.     

Synthèse et désamination enzymatique des C-hydroxyméthyl-3′- et C-méthyl-3′-β-D-xylofurannosyl-9-adénines

Synthesis and enzymatic deamination of 3′-C-hydroxymethyl- and 3′-C-methyl-β-D -xylofuranosyl-9-adenines The title compounds have been prepared by classical synthetic steps after having optimized the nature of the blocking groups. Both nucleosides were found to be substrates of adenosine aminohydrolase which proved that C(3′)-branched-chain sugar nucleosides can be deaminated when the branched-chain is exo (trans relative to the base) if a suitably disposed hydroxy group is available on the endo side of the furanose ring.     

Utilisation d'ylides du phosphore en chimie des sucres VII. Synthèse de sucres ramifiés des types «streptose» et «apiose». Communication préliminaire

A new high-yielding route to branched-chain sugars of the streptose or the apiose type having at the branching point a configuration epimeric with that which would be obtained by the classical synthesis using Grignard reagents is described. The main steps are the preparation of branched-chain unsaturated cyano sugars by reaction of cyanomethylene triphenylphosphorane with keto sugars and the cis-dihydroxylation (KMnO₄) of the so obtained cyano sugars. The cis and the trans isomers of a series of cyanovinylidenic sugars have been separated and the stereodependence of the long-range coupling constants in this class of compounds has been examined.