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.     

Intramolecular nitrile oxide-alkene cycloaddition of sugar derivatives with unmasked hydroxyl group(s)

[reaction: see text] Intramolecular nitrile oxide-alkene cycloaddition (INOC) of sugar derivatives with one to four free hydroxyl group(s) is reported. The INOC reaction, using chloramine-T, in the presence of silica gel, to generate nitrile oxides from oximes, proceeded smoothly to afford five- or six-membered carbocycles in good to excellent yields. This new methodology alleviates protection/deprotection steps and makes the synthetic route shorter and more efficient.     

Synthesis of Less Stable Ketoximes—Regiospecific Substitution of Ketoximes

Dilithium derivatives of ketoximes react with alkyl halides to give α-substituted oximes. The dilithium derivatives are proposed to involve chelate formation. And the product oximes are the less stable (Z-) oximes.     

Furan and Thiophene Oximes: Synthesis, Reactions, and Biological Activity. (Review)

Data on methods for the production of furan and thiophene aldoximes, ketoximes, and amidoximes and their reactions are reviewed. The synthesis of new heterocycles from furan and thiophene oximes and the biological activity of derivatives of the oximes are discussed individually.     

Pyrrole Oximes: Synthesis, Reactions, and Biological Activity. (Review)

Data on the production methods and reactions of pyrrole aldoximes and ketoximes and their derivatives are reviewed. The synthesis of new heterocycles from the pyrrole oximes is examined separately. The principal results from investigation of the biological activity of pyrrole oximes are described.     

Chemoselective coupling of sugar oximes and α-ketoacids to glycosyl amides and N-glycopeptides

The reaction of unprotected sugar hydroxylamines and oximes with α-ketoacids leads to the chemoselective formation of glycosyl amides following the decarboxylative condensation pathway of Bode’s ketoacid hydroxylamine (KAHA) ligation. Sugar oximes with gluco configuration stereoselectively form β-linked products. This method can be used for the convergent synthesis of N-acylated sugars and oligosaccharides bearing small labels, spacers, or peptides in the acyl part.     

Indole and Isatin Oximes: Synthesis, Reactions, and Biological Activity. (Review)

Data on methods for the production of isatin and indole aldoximes, ketoximes, and amidoximes and their reactions are reviewed. Individual syntheses of new heterocycles from indole and isatin oximes are discussed. The principal results from investigation of the biological activity of derivatives of the oximes are also presented.     

Pyridine Oximes: Synthesis, Reactions, and Biological Activity. (Review)

Data on methods for the production of pyridine aldoximes, ketoximes, amidoximes, and their derivatives and their reactions are reviewed. The synthesis of new heterocycles from pyridine oximes is discussed separately. The principal results of research into the biological activity of the oximes are presented.     

Reactivite des gem-dibromocyclopropanes. III (1) : Obtention d'oximes et d'amines α-alleniques

Gem-dibromocyclopropanic oximes are reduced by organolithium derivatives in allenic oximes and by AlLiH₄-AlCl₃ in amines.In one case a 1-hydroxypyrrole is produced.     

An efficient synthesis of phthalocyanines based on an unprecedented double-addition of oximes to phthalonitriles

A novel and efficient method is reported for the preparation of phthalocyanines from phthalonitrile or its derivatives which utilizes low-cost reagents of hydrolytic stability, high simplicity, and easy accessibility, i.e., oximes, and proceeds via an unprecedented double addition of oximes to the nitrile group.     

Synthesis of 3-substituted 5-arylisoxazoles from α,β-unsaturated oximes

The synthesis of 3-substituted 5-arylisoxazoles from oximes of α,β-unsaturated ketones is studied. The formation of the isoxazole derivatives takes place by cyclization of oximes in the presence of iodine and potassium iodide. The presence of isoxazoline is detected. On the basis of the results a plausible mechanism is suggested.     

Conversion of oximes to carbonyl compounds by triscetylpyridinium tetrakis(oxodiperoxotungsto) phosphate (PCWP)-mediated oxidation with hydrogen peroxide

Aromatic and aliphatic oximes have been deoximated in chloroform-water to the corresponding aldehydes with dilute hydrogen peroxide and triscetylpyridinium tetrakis (oxodiperoxotungsto) phosphate as catalyst. The presence of dipolarophiles in the reaction mixtures allows a competitive reaction that converts oximes into isoxazole and isoxazoline derivatives via the intermediate formation of nitrile oxide species.     

Quinoline Oximes: Synthesis,Reactions, and Biological Activity. (Review)

Data on the production and the reactions of quinoline aldoximes and ketoximes and their derivatives are reviewed. The synthesis of new heterocycles based on quinoline oximes is examined separately. The main results from investigation of the biological activity of quinoline oximes are presented.__________Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 163–190, February, 2005.     

肟的无污染氧化

No2;污染治理;二噁烷;肟的无污染氧化     

Acetyl Derivatives of 3-Quinuclidone

Methods have been developed for the synthesis of mono- and bisacetyl derivatives of 2-hydroxyarylmethylene-3-quinuclidone oximes.     

Pyrimidines

The preparation of dimethylacetals and oximes of 2(6)-formyl-4-phenylpyrimidine N-oxides from the corresponding bromomethyl derivatives is described. A syn configuration was assumed for the oximes from the PMR spectra.See [1] for communication LXVI.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1397–1399, October, 1978.     

Pentafluorophenyl complexes of cobalt(III) with 1-(diacetylmonoximatoimino)-3-(diacetylmonoximeimino)-propane (dotnH)

Cyclopalladation of vinylic oximes occurs for the sterically rigid oximes of 1-benzalcyclohexanone and 1-acetylcyclohexene giving dimeric complexes which retain the alkene double bond. The presence of the vinylic palladium bond is shown both by spectroscopic methods and cleavage reactions using carbon monoxide or cyanide ion. The complexes do not make good substrates for the synthesis of vinylic oxime derivatives.     

Oximes of six-membered heterocyclic compounds with two and three heteroatoms. II.* Reactions and biological activity (review)

Data on the reactions of pyridazine, pyrimidine, pyrazine, triazine, oxazine, thiazine, oxadiazine, and thiadiazine aldoximes, ketoximes, and amidoximes and their derivatives are reviewed. The synthesis of new heterocycles based on the oximes of six-membered heterocyclic compounds with two and three heteroatoms is considered separately. The principal results of research into the biological activity of these oximes and their ethers are also presented.     

Recyclization and photorearrangements of 2-acetyl-4,4-dialkyl-2-buten-4-olide oximes

Recyclization to derivatives of dihydro-1,2-oxazines was realized by the reaction of 2-acetyl-3-methyl-4,4-dialkyl-2-buten-4-olide oximes with sodium borohydride. The UV-irradiation-initiated Beckmann rearrangement of the oximes cited above leads to 4,4-dialkyl-2-buten-4-olide-2-carboxylic acid N-methylamides.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 157–160, February, 1989.     

Synthesis of aldehydes and nitriles in the 5-hydroxyindole series

A preparative method for the synthesis of previously inaccessible 3-formyl-5-hydroxyindole derivatives by Vilsmeier formylation of 5-acetoxyindoles is proposed. 5-Hydroxyindole-3-carboxylic acid nitriles and their 4-dimethylamino-methyl derivatives were obtained from 3-formyl-5-hydroxyindoles through their oximes.