The Reduction of Acetylated Glycopyranosyl Bromides to 1,5-Anhydroglycitols with Lithium Aluminum Hydride. 1,5-Anhydro-L-rhamnitol

Ness, Robert K.; Fletcher, Hewitt G.; Hudson, C. S.

doi:10.1021/ja01166a059

Cited by 82 publications

(18 citation statements)

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“…[13,42] The synthetic interest stems from the fact that 20 presumably represents the biosynthetic precursor of the antibiotic Microthecin, [11b] and that it may be used for synthetic purposes. [40,41,43] From the oxidation with pyranose oxidase we isolated 1,5-anhydro-d-fructose (20) in a yield of 98 %; the product is thus available in three steps from d-glucose via 2,3,4,6-tetra-O-acetyl-a-d-glucopyranosyl bromide, reduction at position 1, [44] and enzymatic oxidation in an overall yield of approximately 60 %. When the enzymatic oxidation was prolonged a product of dioxidation formed in 33 % yield.…”

Section: Substratementioning

confidence: 99%

Rare Keto-Aldoses from Enzymatic Oxidation: Substrates and Oxidation Products of Pyranose 2-Oxidase

Freimund¹,

et al. 1998

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Pyranose oxidases are known to oxidise d-glucose, d-xylose and lsorbose to keto-aldoses, biochemically interesting compounds that may also be used for synthetic purposes in a variety of reactions. In this study pyranose oxidase from the basidiomycete Peniophora gigantea was investigated, and it was found that this enzyme is able to oxidise a broad variety of substrates very effectively. In analogy to its natural mode of action, most substrates are oxidised regioselectively in position 2. Certain compounds, however, are converted into 3-keto derivatives, and the enzyme even exhibits transfer potential, that is, disaccharides are formed from bglycosides of higher alcohols. Substrates that may be oxidised at C-2 in yields between 40 ± 98 % are d-allose, d-galactose, 6-deoxy-d-glucose, d-gentiobiose, a-d-glucopyranosyl fluoride and the very interesting 3-deoxy-d-glucose. 1,5-Anhydro-d-glucitol (1-deoxy-d-glucose) is very effectively oxidised in position 2 in 98 % yield and additionally gives a product of dioxidation at C-2 and C-3 upon prolonged reaction time. Selective oxidation at C-3 was found for 2-deoxyd-glucose in very good yields and for methyl b-d-gluco-and methyl b-galactopyranoside in lower yields. All oxidation products were unequivocally characterised by NMR spectroscopy and/or chemical derivatisation. In addition, the kinetic data of the enzymatic reactions were determined for all substrates. On the basis of these data and the structural characteristics of the substrates, a model for the minimal structural requirements of the enzyme ± substrate interaction is suggested. The enzyme presumably uses two different binding modes for the regioselective C-2 and the C-3 oxidations, which are described.

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Section: Substratementioning

confidence: 99%

Rare Keto-Aldoses from Enzymatic Oxidation: Substrates and Oxidation Products of Pyranose 2-Oxidase

Freimund¹,

et al. 1998

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“…Coupling of 9 with perbenzoylated glucosyl bromide 17 [16] stereoselectively gave the β(1Ǟ4)-linked disaccharide 18 (89%), the benzoyl group of which was replaced with acetyl group by Zemplén transesterification (to give 19; 99%) and conventional acetylation with acetic anhydride and pyridine (96%) to give 20. Removal of the isopropylidene acetal in 20 afforded the 2,3-diol 21 (96%), which was then glycosylated with 16 to give mainly the 2-O-glycosylated derivative (about 60%; data not shown).…”

Section: Resultsmentioning

confidence: 99%

Synthetic Study on Campylobacter jejuni Lipopolysaccharides: An Improved Synthesis of a Branched, Heptose‐Containing Trisaccharide Core Structure and Its Conversion into Ganglioside GD3 Related Hexasaccharide

et al. 2003

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“…1,s-anhydroglucitol and 1,s-anhydromannitol were synthesized by the method of Ness et al (1950). These were similarly undermethylated and acetylated to produce mixtures of standards.…”

Section: Electroporation Of Cke5 a Xylinum Was Grown In Hs Brothmentioning

confidence: 99%

Generation of a novel polysaccharide by inactivation of the aceP gene from the acetan biosynthetic pathway in Acetobacter xylinum

Edwards¹,

Colquhoun²,

Morris³

et al. 1999

Microbiology

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The acetan biosynthetic pathway in Acetobacter xylinum is an ideal model system for engineering novel bacterial polysaccharides. To genetically manipulate this pathway, an Acetobacter strain (CKES), more susceptible to gene-transfer methodologies, was developed. A new gene, aceP, involved in acetan biosynthesis was identified, sequenced and shown to have homology at the amino acid level with /?-D-glucosyl transferases from a number of different organisms. Disruption of aceP in strain CKE5 confirmed the function assigned above and was used to engineer a novel polysaccharide with a pentasaccharide repeat unit.

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The Reduction of Acetylated Glycopyranosyl Bromides to 1,5-Anhydroglycitols with Lithium Aluminum Hydride. 1,5-Anhydro-L-rhamnitol

Cited by 82 publications

References 0 publications

Rare Keto-Aldoses from Enzymatic Oxidation: Substrates and Oxidation Products of Pyranose 2-Oxidase

Rare Keto-Aldoses from Enzymatic Oxidation: Substrates and Oxidation Products of Pyranose 2-Oxidase

Synthetic Study on Campylobacter jejuni Lipopolysaccharides: An Improved Synthesis of a Branched, Heptose‐Containing Trisaccharide Core Structure and Its Conversion into Ganglioside GD3 Related Hexasaccharide

Generation of a novel polysaccharide by inactivation of the aceP gene from the acetan biosynthetic pathway in Acetobacter xylinum

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