Synthesis of 6-Deoxy-D-manno-heptose.

Borén, Hans; Eklind, Karin; Garegg, Per J.; Lindberg, Bengt; Pilotti, Åke

doi:10.3891/acta.chem.scand.26-4143

Cited by 64 publications

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“…The residual syrup in acetonitri1e:water (9:1, 30 mL) was treated with potassium cyanide (0.24 g, 3.68 mmol) for 2.5 h at room temperature, the solution was concentrated, and the residue was dissolved in ethyl acetate, washed successively with 1 M HC1, aqueous saturated NaHC03, and water, dried, and concentrated. The residual syrup was chromatographed on silica gel (light petroleum -ethyl acetate, 3.5: 1) to give compound 2 (0.9 g, 82%), [aID +85 (c 1.35); ir v , , , : 2250 ( e N ) cm-'; 'H nmr 6: 4.68-4.26 (m, 8H, H-1, H-5, 3 x CH2Ph), 3.81 (t,IH,3.71 (d,lH,3.61 (3.61 (dd,lH,J3,4 3.0 Hz,J4,5 9.66 Hz),3.42 (s,3H,OMe),2.80 (dd,IH,J5.6 3.08 Hz,J6,6' 16.7 Hz,, and 2.5 (dd,lH,J5,6,8.3 Hz,. Anal.…”

Section: Derivatives Of 6-deoxyheptoses For Glc and Glc-ms Analysismentioning

confidence: 99%

“…Garegg, Lindberg, and co-workers (6,7) have reported syntheses of 6-deoxyheptoses with the D-manno and D-galacto configurations by homologations at C-6 of the corresponding methyl 2,3,4-tri-0-benzyl-hexodialdo-1,5-pyranosides by reaction with methoxymethylenetriphenylphosphorane, but with rather unsatisfactory yields. We describe here an alternative approach with the cyanide displacement of 2,3,4-tri-0-benzyl-a-~-glycopyranoside 6-sulfonate esters used by Baer et al (8) in the preparation of 6-deoxy-D-gluco-heptopyranosidurononitriles, followed by a two-step reduction involving treatment with diisobutylaluminum hydride (DIBAH), hydrolysis of the resulting imine, and further reduction with sodium borohydride.…”

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confidence: 99%

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Syntheses of methyl glycosides of 6-deoxyheptoses

Aspinall¹,

McDonald²,

Sood³

1994

Can. J. Chem.

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Methyl a-D-glycopyranosides of 6-deoxy-D-altro-heptose, 6-deoxy-D-n~anno-heptose, and 6-deoxy-D-talo-heptose have been prepared. Displacements of methyl 2,3,4-tri-0-benzylhexopyranoside 6-trifluoromethanesulfonates with potassium cyanide, followed by reduction of the resulting heptopyranosidurononitriles with diisobutylaluminurn hydride, hydrolysis of the imine, further reduction with sodium borohydride, and catalytic 0-debenzylation, give the corresponding methyl 6-deoxyheptopyranosides. Configurational change at C-4 of methyl 6-deoxy-7-O-tert-butyldiphenyIsilyl-a-~-rt1anno-heptopyranoside to give the talo isomer was effected by oxidation followed by stereoselective reduction. 'H nuclear magnetic resonance data of the glycosides, and gas chromatography of acetylated glycosides of (R)-and (S)-2-butanol serve to establish ring and enantiomeric configurations of the parent sugars when these are encountered as constituents of lipopolysaccharides or extracellular carbohydrate polymers, as in Carnpylobacter species.GERALD 0. ASPINALL, AWNDO G. MCDONALD et RAMESH K. SOOD. Can. J. Chem. 72,247 (1994).On a prepare les a-D-glycopyranosides de mCthyle des 6-dCsoxy-a-D-altro-heptose, 6-dCsoxy-D-manno-heptose et 6-dCsoxy-D-talo-heptose. Les dCplacements des 6-trifluoromCthanesulfonates des 2,3,4-tri-0-benzylhexopyranosides de rntthyle par le cyanure de potassium, suivis par la rtduction des heptopyranosidurononitriles par l'hydrure de diisobutylaluminium, une hydrolyse de I'imine, une nouvelle rCduction par le borohydrure de sodium et finalernent une 0-dCbenzylation catalytique conduit aux 6-dtsoxyheptopyranosides de mCthyles correspondants. Pour effectuer un changement de configuration en C-4 du 6-dCsoxy-7-O-tert-butyldiphCnylsilyl-a-o-rnanno-heptopyranoside de mCthyle dans le but d'obtenir l'isomttre ralo, on a procCdC j. une oxydation suivie par une rCduction sClective. On a fait appel aux donntes de la resonance magnktique nuclCaire du 'H des glycosides et ti la chromatographie gazeuse des glycosides acCtylCs par les (R)-et (S)-2-butanol pour Ctablir la grandeur des cycles et les configurations Cnantiombes des sucres parents rencontrCs comme constituants des lipopolysaccharides ou comme hydrates de carbones polymCriques extracellulaires, comme dans les especes Campylobucter.[Traduit par la rCdaction]

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Section: Derivatives Of 6-deoxyheptoses For Glc and Glc-ms Analysismentioning

confidence: 99%

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confidence: 99%

Syntheses of methyl glycosides of 6-deoxyheptoses

Aspinall¹,

McDonald²,

Sood³

1994

Can. J. Chem.

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“…Moreover, the possible attachment of drugs to sugar phosOne pathway led to the isosteric compound 1, while the other led to a non-isosteric analog 2, which possesses one [a] Laboratoire de Chimie Biomoléculaire CC073, Université Montless carbon atom between its phosphorus atom and the supellier II, gar moiety. In both cases, the alcohol 3 [7] is the starting Place Eugène Bataillon, F-34095 Montpellier cedex 05, France E-mail: morere@univ-montp2.fr compound (Scheme 1). montero@univ-montp2.fr For the synthesis of the mannose 6-phosphate isoster 1, [b] Unité Hormones et Cancer (U148), INSERM, 60, rue de Navacelles, F-34090 Montpellier, France we followed the strategy described in Scheme 2.…”

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confidence: 99%

“…The organic layer was then concentrated before the adlished procedures. [7,11] Ϫ The cation exchange resin (50WX2 H ϩ Dowex) was washed with a 1  NaOH solution and then with dition of 60 mL of distilled water and 30 g of cation exchange resin. After stirring at room temp.…”

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confidence: 99%

Synthesis and Biological Activity of Phosphonate Analogs of Mannose 6-Phosphate (M6P)

Vidil

Morére²,

Garcia

et al. 1999

Eur. J. Org. Chem.

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Two phosphonate analogs of mannose 6‐phosphate (M6P) have been synthesized. The isosteric analog 1 was obtained by a Wittig–Horner reaction at position 6 of a sugar aldehyde. The non‐isosteric analog 2 was obtained by a Michaelis–Arbuzov rearrangement of a 6‐bromo derivative. In contrast to the non‐isosteric analog 2, the isoster 1 was shown to bind to M6P receptors as effectively as does M6P itself, thus demonstrating the considerable potential of the system in drug design.

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“…The pentane triol 6 was successively converted to 1 -anthroyl ester 7, then to 2,3 bis paramethoxycinnamoyl ester 8 as described by Nakanishi'. The global yield of these reactions was 60% after purification of the products by chromatography and preparative thin layer chromatography.…”

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confidence: 99%

Exiton Chirality Method: A Tool for the Chirality Determination of 7,8‐dideoxy‐l‐glycero‐d‐manno‐oct‐7‐ynopyranose

Elloumi

Aguiar

Capmau

1994

Bulletin des Soc Chimique

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dichroi'sm after derivatisation.A pyranose pathway degradation leads to a 1,2,3-pentane triol, configuration of which can be confirmed by circular It is well established that L-glycero-D-manno-heptopyranose is an important component of the core region of many polysaccharides of Gram negative bacterial. In order to synthesize this compound, various groups have realized many suitable nucleophilic additions on conveniently protected D-manno-hexodialdopyranoside. Thus, K. Dziewiszck and A. Zamojski2 described CI extension of D-mannopyranose by treatment of methyl 2,3,4-tri-0-benzylu-D-mannohexodialdo-l,5-pyranoside with hydrogen cyanide; the reaction was not stereospecific. A great stereospecificity was observed in this series only with organomagnesium compounds as nucleophilic reagents : G.J.P.H. Boons and coL3 have obtained a stereospecificC1 extension of D mannose using isopropoxydimethylsilylmagnesium bromide on the same aldehyde as reported also by Garegg and coL4 A Cp stereospecific extension of D-mannose was also described by Chapleur and coL5 using vinyl magnesium bromide on methyl 2,3-O-isopropylidene-4-O-benzylu-D-mannohexodialdo-l,5-pyranoside.The unique compound obtained in each of these experiments can be transformed in L-glycero-Dmannoheptopyranose. Its respective configuration was proved by filiation with diethyl dithioacetal of L-glycero-Dmannoheptose6 or by NMR spectroscopy of an adequate bis cyclic aceta15. We have prepared stereospecifically the methyl 2,3,4-tri-O-benzyl-7,8-dideoxy-L-glycerou-Dmanno-oct-7-ynopyranoside 2 with a good yield (90%) by reaction of ethynylmagnesium bromide at -1 0" in tetrahydrofuran on methyl-2,3,4-tri-O-benzyla-D-mannohexodialdopyranoside 1. This new compound could also be transformed in L-glycero-D-mannoheptopyranose. Here we report the procedure used for the determination of its configuration, because this procedure could be applied to compounds resulting of a C2 homologation of any alkyl hexodialdo-l,5-pyranoside.Catalytic hydrogenation of the methyI-2,3,4-tri-Obenzyl-7,8-dideoxy-glycero-a-D-manno-oct-7-ynopyranoside 2 with palladium on carbon (10%) in ethanol gave methyl-7,8-dideoxy-L-glycero-~z-D-mannopyranoside 3. Periodic oxydation of 3 led to a dialdehyde 4, which was not separated but visualized on thin layer chromatography. This aldehyde was reduced to the complex triol 5 which after acid hydrolysis gave the pentane triol 6. The yield was 80% from the starting material 2 (Scheme 1).The pentane triol 6 was successively converted to 1 -anthroyl ester 7, then to 2,3 bis paramethoxycinnamoyl ester 8 as described by Nakanishi'. The global yield of these reactions was 60% after purification of the products by chromatography and preparative thin layer chromatography. Careful analysis showed that a unique product resulted from each esterification*. The triester was characterized by its NMR spectrum and its elementaryanalysis. It showed a characteristic circular dichroi'sm curve (CD) (Scheme 2) proving a 2R,3S configuration for the pentane triol 6; carbon 3 ...

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Synthesis of 6-Deoxy-D-manno-heptose.

Cited by 64 publications

References 0 publications

Syntheses of methyl glycosides of 6-deoxyheptoses

Syntheses of methyl glycosides of 6-deoxyheptoses

Synthesis and Biological Activity of Phosphonate Analogs of Mannose 6-Phosphate (M6P)

Exiton Chirality Method: A Tool for the Chirality Determination of 7,8‐dideoxy‐l‐glycero‐d‐manno‐oct‐7‐ynopyranose

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