Nouveaux exemples d'acétonides d'aldéhydosucres furanniques

Further examples of O-isopropylidenaldehydosugars in the furanose series Formyl-bearing furanose derivatives 1–3 (α-D -xylo or α-D -erythro configurations) and 5–8 (configurations α-D -ribo, α-D -lyxo, β-L -threo and D -arabino) have been prepared by classical synthetic steps and their properties mainly spectroscopic, reported. The coupling constant between the formyl and the vicinal proton is always small. Like other members of the series, these new aldehydosugars constitute very useful and flexible synthetic intermediates.     

Chemistry and pharmacology of apiose. Synthesis of hydroxymethyl-3-beta-L-erythrofurannosyl-9-adenine

A synthesis of the L enantiomer of a very close analog of adenosine is described. Some properties of that compound are compared with those of the D enantiomer of its 3-epimer which has also been prepared.     

Synthèse de nouveaux types de dérivés C-glycosyliques à partir de sucres acétyléniques ou de leurs équivalents synthétiques partiels

Synthesis of Novel Types of C-Glycosyl-derivatives from Acetylenic Sugars or Partial Synthetic Equivalents thereof The concept of synthetic equivalent is not unequivocal and, for example, α-fluoroenamines may behave in some cases as synthetic equivalents of ynamines and, in other situations, quite differently. Some uses of these α-fluoroenamines, ‘partial synthetic equivalents’ of ynamines, for the synthesis of C-glycosyl derivatives of coumarins, chromones, quinolines, quinolones, thietenes and isoxazoles are described. We also report the preparation of a series of mono- and diglycosylthiophenes by reacting HS^? with mono- and diglycosylbutadiynes. Acetylenic sugar derivatives have also been used for the synthesis of a diglycosylazaphosphorine and a spirooxolenone.     

Enaminosucres et sucres halogénoacétyléniques. Communication préliminaire

Enamino- and Halogenoacetylenic sugars Traitment of an aldehydosugar ( 1 ) with secondary amines gave in an essentially quantitative yield the expected enamines ( 4–6 ). Chloro- and bromo-acetylenic sugars ( 11–14 ) were obtained in good yields by reacting with lithium methylphenylamide the corresponding gem-dihalo-olefinic sugars ( 7–10 ), whereas a Z-gem-fluoro-enamine ( 17 ) was formed when the difluoro-olefinic sugar 15 was submitted to the same reaction. The fluoro-enamine 17 is a useful synthetic intermediate allowing the preparation of several kinds of C-glycosylic compounds bearing heterocycles like isoxazole, chromone or coumarin.     

Etude par spectrométrie de masse de la fragmentation du désoxy-3-di-O-isopropylidène-1,2: 5,6-méthylidène-3-α-D-hexofurannose et de quelques analogues substitués en C(3′)

Electron Impact Mass Spectrometry of the 3-Desoxy-1,2: 5,6-di-O-isopropylidene-3-methylidene-δ-D -hexofuranose and Some C(3′)-Substituted Analogues The mass spectra of the 3-desoxy-1,2:5, 6-di-O-isopropylidene-3-methylidene- α-D -ribo-hexofuranose and of some C(3′)-mono- and -disubstituted derivatives have been investigated. Deuterium labelled molecules allow fragmentation modes to be proposed.     

Experimental and computational studies of trialkylaluminum and alkylaluminum chloride reactions with silica

Reactions of trimethylaluminum, triethylaluminum, and diethylaluminum chloride and ethylaluminum dichloride with silica gel have been studied experimentally by infrared spectroscopy and elemental analysis. The silica gel was subjected to different pretreatments to alter surface functionalities prior to reaction. In all cases the extent of surface modification reaction follows the trend unmodified > 600 degrees C pretreated > hexamethyldisilazane (HMDZ) pretreated > 600 degrees C/HMDZ pretreated. All of the aluminum compounds studied completely react non-hydrogen-bonded silanols, while also reacting with hydrogen-bonded silanols and siloxanes. Primarily monomeric surface species result from the surface modification reaction. Ethylaluminum chlorides preferentially react with silanols through cleavage of the Al-C bond rather than the Al-Cl bond. Singly bonded Si(s)-O-AlCl(2) surface species are readily synthesized by reaction of ethylaluminum dichloride with HMDZ-pretreated silica gel. Bridged bonded (Si(s)-O)(2)-AlCl surface species are readily synthesized by reaction of diethylaluminum chloride with HMDZ-pretreated silica gel. Computational ab initio studies of the cluster Si(4)O(6)(OH)(4) as a model to study the reaction of monomeric and dimeric methylaluminum dichloride with a silica silanol are also described. Comparison of the potential energy surface (PES) of monomer and dimer indicates that the energetics favor monomer reaction, consistent with experimental results. The energy cost in the dimer reaction is primarily from cleavage of a bridged Al-Cl bond upon adsorption. This does not occur when the monomer adsorbs. A comparison of the PES for the two reaction pathways resulting from cleavage of either an Al-Cl or Al-C bond indicates that while the former reaction is slightly kinetically favored (E(a) = 23.1 kJ/mol for Al-Cl bond cleavage versus E(a) = 31.1 kJ/mol for Al-C bond cleavage), the latter is strongly thermodynamically favored with an overall free energy difference between the two reaction pathways of 135 kJ/mol favorable to Al-C bond cleavage. These reactions are thermodynamically controlled.     

Synthesis and Structural Assignment of 1-O-Acetyl-2,3,5-tri-O-benzoyl-4-(thymin-1-yl)-α-l-lyxofuranose

Abstract

Analogues of nucleosides in which the nucleobase is fixed onto the C-4 of the sugar moiety are generally prepared either from 4,5-unsaturated sugar derivatives or via a formaldehyde condensation.¹ We tested the furanosyl bromide reactivity of 1 ² towards a series of nucleophiles, mostly azides or cyanides, without success. Conversely, the nucleosidation of 1 using 5-methyl-2,4-bis(trimethyl-silyloxy)pyrimidine in the presence of stannic chloride took place at the second anomeric position (C-4) and led to the isolation in acceptable yield (47%) of a unique anomer 2 (Scheme 1).     

Derivatives of 3-Deoxy-3-(N-Hydroxyamino)-D-Ribose

Abstract

A series of 3-(N-arylmethyl-N-hydroxyamino)-l,2-O-cyclopentylidene-3-deoxy-5-O-toluoyl-α-D-riboses has been prepared. The blocking groups used were chosen to allow an easy nucleosidation of these compounds to spin labelled analogs of natural nucleosides. The conformational behavior of the N-arylmethyl-N-hydroxyamino group has been studied using ³/_CH NMR coupling data and molecular mechanics computations. Upon spontaneous oxidation, these hydroxylamines led to the corresponding aminoxyl free radicals which were submitted to EPR spectroscopy and quantum mechanical computations at a semiempirical level (PM3).     

Some Physico-Chemical and Biological Properties of Triazeno Sugars

Replacement of the alkyl group of l-aryl-3-alkyltriazenes with a sugar moiety did not significantly modify their tautomeric behaviour. The same replacement done on 1-aryl-3-alkyl-3-methyl-triazenes did not affect to any large extent their rotameric properties. In contrast, the most prominent biological properties, anticancer activity and toxicity, of 1-aryl-3-methyltria-zenes disappeared on replacement of the methyl group with a sugar moiety. Unexpectedly, the N-acetyltriazene 15 was highly cyto-toxic.     

From Pyranosuloses and Pyranosenuloses to Deoxy Hydroxyamino Sugars

Abstract

Deoxy hydroxyamino sugars represent a potentially useful series of sugar analogs owing mainly to the fact that they oxidize spontaneously to nitroxide free radicals to give spin-labeled sugar derivatives whose structure is very close to that of the parent sugar.₃ We describe herin two synthetic pathways towards these compounds, reduction of sugar oximes and conjugate addition to enolones derivatives, both in the pyranose series.