D-Mannose oxime

D- rafro-Tetrahydroxybutyl)pyrazine 1-oxide (7) has been prepared by Fujii and Kobatake (543, 544) by the condensation of 2-amino-2-deoxy-D-glucose oxime (6) or 2-amino-2-deoxy-D-mannose oxime with glyoxal in water at room temperature. 

Beckmann rearrangement of the o-mannono-l,4-lactone oxime derivative 1046, obtained by oxidation of the aldehydo-D-mannose oxime derivative 1045, with butyllithium followed by treatment with phosphorus pen-tachloride gave the 2-chloro-4,5-dihydro-l,3-oxazin-6-yl acyclo C-nucleoside 1047 (85HCA2254) (Scheme 302). 

In a reinvestigation of the synthesis of aldononitrile peracetates from sugars by oximation and acetylation, it was shown that (a) peracetylated acyclic oximes are present in the product mixtures, but are converted to the nitriles by elimination of acetic acid in the heated injection port during GLC analysis and (b) less of the peracetylated A-hydroxyglycosylamine byproduct is formed using 1-methylimi-dazole as a catalyst. The fate of 2,3 5,6-di-0-isopropylidene-D-mannose oxime, which can exist as its cyclic AT-hydroxy-a-D-mannofuranosylamine tautomer, on... 

The oxime of D-lyxose has not been prepared, but L-rhamnose oxime (XX) with ithe same spatial configuration about carbon atoms 2, 3 and 4 reacts in an open-chain form when submitted to mild acetylation, and gives only the nitrile this reactivity is confirmed when the oxime is submitted to mild propionylation, for only the hexapropionyl-aWe%do-L-rhamnose oxime is produced and that in high yield. As already mentioned, the oximes of D-mannose (XXI), and D-gala-L- reawno-heptose (XXII),having the same configuration as rhamnose about carbon atoms 2, 3 and 4, react in a similar manner. 

The first benzoylated nitrile of an aldonic acid was prepared by Brigl, Muhlschlegel and Schinle by benzoylation of the n-manno-n- oZa-heptononitrile the hexabenzoyl derivative was obtained. A series of benzoylated nitriles has recently been prepared by Restelli de Labriola and Deulofeu by treatment of the oximes of L-rhamnose, D-glucose, D-galactose and D-mannose with benzoyl chloride and pyridine. They were the sole products and were obtained in high yields. 

An Nitrone lassen sich Alkene 1,3-dipolar addieren. Dies nutzt eine asymmetrische Syn-these von L-5-Oxa-prolin aus. Das Nitron aus 2,3 5,6-Di-0-isopropyliden-mannose-oxim mit Glyoxylsaure-tert.-butylester in situ) cyclisiert mit Ethen, wobei das (JS)-Dihstereo-mer spontan kristallisiert (3R)- bzw. (3S)-3-tert.-Butyloxycarbonyl-2-(2,3 5,6-di-0-iso-propyliden-ct-D-mannofuranosyl) l,2-oxazolidin[9i%, 54% de (S43%].Nachder Abspaltung des Aldose-Restes erhalt man (S)-5-Oxa-prolin-tert.-butylester (3-tert.-Butyl-oxycarbonyl-1,2-oxazolidin 90% Schmp. 52-530)4 ... 

In parallel fashion, compound 267, made from 2,3 5,6-di-<9-isopropyl-idene-D-mannono-1,4-lactone by Reformatsky addition using ethyl bromo-acetate and zinc-silver graphite, undergoes ready elimination when converted to the methanesulfonic ester to give a separable mixture of the E- and Z-alkenes (268).251 Quite a different approach involves treatment of the 1-C-nitromannofuranosyl chloride, derived from the oxime of 2,3 5,6-di-O-isopropylidene-D-mannose, with the anion of diethyl malonate to give the disubstituted alkene 269.252... 

An asymmetric synthesis of aminocyclopentitols 134-137 has been used in the synthesis of trehazolin via free-radical cycloisomerization of enantiomerically pure, alkyne-tethered oxime ethers derived from D-mannose (Scheme 17).84 Treatment of 2,3 5,6-di-(9-isopropylidene-D-mannofuranose (128)85 with ethynylmagnesium bromide gave compound 129, which underwent sequential one-pot acid hydrolysis plus diol cleavage to give 130, oximation of which afforded the radical precursor 131, in 41% overall yield from 129. The free hydroxyl group of 131 was protected as acetate 132 and tert-butyldimethylsilyl ether 133, which were isolated as inseparable... 

D-Mannose 2,3 5,6-Di-0-isopropyli-dene- -oxim- E21f, 5930 (OH/OR -> Oxim)... 

SUBSTITUTED PYRAZINE 1-OXIDES FROM 2-AMINO-2-DEOXY-D-GLUCOSE (OR MANNOSE) OXIME WITH GLYOXAL... 

Preparations of pyrazine A -oxides containing extranuclear hydroxyl groups are also described in Qiapter III as follows Section III.l, 2-aminopyrazine 1-oxides from a-amino nitriles and a-hydroxyimino carbonyl compounds (540, 541) Section III.2, 3-substituted pyrazine 1-oxides from 2-amino-2-deoxy-D-glucose(or mannose) oxime with glyoxal (543, 544) and Section III.5, ring closure of the C-C-N-C-C-N-0 system (553). 

PAMAM scaffolds have been decorated with carbohydrates via oxime ligation [177], RAFT scaffolds have been functionalized with D-mannose, /V-acetylga-lactosamine and lactose via the reversed oxime ligation, i.e. the sugar molecules were aminoxylated (cf. Scheme 1) and then reacted in aqueous acetic acid with the RAFT scaffold provided on solid support and presenting four glyoxaldehyde functions. Excess sugar was recovered and RP-HPLC analysis of a reaction sample, cleaved from the resin, showed only the expected product [72],... 

Hydrogenation of aldose oximes (aldoses D-arabinose, D-mannose and D-galactose) at 50 °C over 5 % Pt/C catalyst, under 100 bar hydrogen, resulted in quantitative conversion of the oximes to a mixture of mono- and dialditylamines from which the latter were isolated in fairly good yield (26-80%) [44]. 

The similar polarographic behavior of semicarbazones, hydrazones, phenylhydrazones, and oximes of D-glucose, D-galactose, and n-mannose was described in another paper. For the aldoses studied, the equilibrium and rate constants for the formation of their oximes, semicarbazones, and hydrazones were determined at several different pH values, and it was found that their reactivity increases in the order D-glucose < D-galactose < D-mannose < D-xylose < n-arabinose < D-ribose < D-lyxose. ... 

Glycosylamines and Glycosylammonium Salts. - X-Ray crystallography has shown that iV-phenyl-, iV-4-chlorophenyl- and iV-carboxamido-D-man-nosylamine are in the P-pyranosyl form in the solid state, whereas mannose oxime is in the open chain form. The conclusion from an examination of the conformations of various 2,3,4,6-tetra-O-acetyl-iV-aryl-D-glucopyanosylamines in neutral and protonated form was that there was no evidence to support the existence of a reverse anomeric effect. ... 

Cu2Cl2-py) have been used to convert aldose oximes into aldono-lactone oximes. Free sugar oximes gave products such as the D-gluco example (52) with a Z-confIguration, whereas 2,3 5,6-dl-O-Isopropylidene-D-mannose yields an E/ mixture (c.f. V0I.I6, p.lll... 

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