Synthesis of (6R)- and (6S)-<scp>d</scp>-Glucose-6-2H through Stereospecific Photo-bromination of 1,6-Anhydro-β-<scp>d</scp>-glucopyranose Derivative

Ohrui, Hiroshi; Horiki, Hiroyuki; Kishi, Hisashi; Meguro, Hiroshi

doi:10.1080/00021369.1983.10865756

Cited by 7 publications

(8 citation statements)

References 3 publications

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“…The 6 S -deuterio-1,6-anhydroglucose derivative ( 11 ) 34,35,43 was the starting material for the preparation of 6 S - d -3 . Thus, 11 was converted to the thioglycoside 12 by cleavage of the 1,6-anhydro bridge with trimethylsilyl ethanethiol in the presence of zinc iodide 45 followed by acetylation (Scheme 2).…”

Section: Resultsmentioning

confidence: 99%

Interplay of Protecting Groups and Side Chain Conformation in Glycopyranosides. Modulation of the Influence of Remote Substituents on Glycosylation?

2018

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The synthesis and conformational analysis of a series of phenyl 2,3,6-tri-O-benzyl-β-d-thio galacto- and glucopyranosides and their 6S-deuterio isotopomers, with systematic variation of the protecting group at the 4-position, are described. For the galactopyranosides, replacement of a 4-O-benzyl ether by a 4-O-alkanoyl or aroyl ester results in a small but measurable shift in side chain population away from the trans,gauche conformation and in favor of the gauche,trans conformer. In the glucopyranoside series on the other hand, replacement of a 4-O-benzyl ether by a 4-O-alkanoyl or aroyl ester results in a small but measurable increase in the population of the trans,gauche conformer at the expense of the gauche,gauche conformer. The possible modulating effect of these conformational changes on the well-known changes in the anomeric reactivity of glycosyl donors as a function of protecting group is discussed, raising the possibility that larger changes may be observed at the transition state for glycosylation. A comparable study with a series of ethyl 2,3,4-tri-O-benzyl-β-d-thioglucopyranosides reveals that no significant influence in side chain population is observed on changing the O6 protecting group.

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Section: Resultsmentioning

confidence: 99%

Interplay of Protecting Groups and Side Chain Conformation in Glycopyranosides. Modulation of the Influence of Remote Substituents on Glycosylation?

2018

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“…Epimerization of the C(6) methylene hydrogens during reactions (v) to (vii) was ruled out by synthesis of stereospecifically deuterated glucose. (6S) ‐1,6‐Anhydro‐2,3,4‐tri‐ O ‐benzoyl‐ β ‐ D ‐glucopyranose‐6‐D was synthesized according to (Ohrui et al 1983), and was hydrolysed to (6S) ‐1,6‐anhydro‐ β ‐ D ‐glucopyranose‐6‐D. This was reacted directly, according to steps (v) and (vi), to yield (6S) ‐1,2‐ O ‐isopropylidene‐ α ‐ D ‐glucofuranose‐6‐D.…”

Section: Methodsmentioning

confidence: 99%

Intramolecular deuterium distributions reveal disequilibrium of chloroplast phosphoglucose isomerase

Schleucher

Vanderveer

Markley³

et al. 1999

Plant Cell & Environment

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Intramolecular deuterium distributions of the carbonbound hydrogens of glucose were measured using deuterium nuclear magnetic resonance. Glucose isolated from leaf starch of common bean (Phaseolus vulgaris cv. Linden) or spinach (Spinacia oleracea cv. Giant nobel) was depleted in deuterium in the C(2) position, compared with glucose isolated from leaf sucrose or bean endosperm starch. In beans, the depletion of C(2) was independent of the light intensity during growth (150 or 700 µmol photons s -1 m -2 ). The ratio of glucose-6-phosphate to fructose-6-phosphate ([G6P]/[F6P]) in bean chloroplasts was 0·9 in high light, indicating that the phosphoglucose isomerase reaction was not in equilibrium ([G6P]/[F6P]) ≈ 3). This implies that the kinetic isotope effect of phosphoglucose isomerase depleted deuterium in the C(2) position of G6P. Because the depletion was the same, the chloroplastic ([G6P]/[F6P]) ratio was in disequilibrium irrespective of the light intensity. If the ([G6P]/[F6P]) ratio was in equilibrium, a large chloroplastic pool of G6P would be unavailable for regeneration of ribulose-1,5-bisphospate. We argue that chloroplast phosphoglucose isomerase activity is regulated to avoid this. The deuterium depletion of C(2) explains the known low overall deuterium abundance of leaf starch. This example shows that measurements of intramolecular deuterium distributions can be essential to understand overall deuterium abundances of plant material.

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“…7–10 Accordingly, white light stimulated bromination of 1,6-anhydro-D-glucopyranose triacetate 6 in α,α,α-trifluorotoluene 11 gave 78% of the 6-exo-bromide 7 , which was reduced with tributyltin deuteride in hot toluene to give the 6-exo-deuterio 1,6-anhydroglucose 8 in 82% yield (Scheme 1). Zemplen deacetylation then gave a triol which on reaction with toluenesulfonyl chloride in pyridine gave the 2,4-di- O -tosylate 9 in 82% yield for the two steps.…”

Section: Resultsmentioning

confidence: 99%

Stereospecific synthesis of methyl 2-amino-2-deoxy-(6S)-deuterio-α,β-d-glucopyranoside and methyl 2,6-diamino-2,6-dideoxy-(6R)-deuterio-α,β-d-glucopyranoside: Side chain conformations of the 2-amino-2-deoxy and 2,6-diamino-2,6-dideoxyglucopyranosides

Kato

Vasella

Crich

2017

Carbohydrate Research

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The stereospecifically labeled 6-monodeuterio methyl 2,6-diamino-2,6-dideoxy-α- and β-D-glucopyranosides were synthesized with a view to determining their side chain conformations. NMR studies in D2O at pH 5 and pH 11 reveal both anomers to adopt very predominantly the gt conformation consistent with the gauche conformation of 2-aminoethanol and its acetate salt. In contrast, as also revealed with the help of stereospecifically-labelled monodeuterio isotopomers, the methyl 2-amino-2-deoxy-α- and β-D-glucopyranosides are an approximately 1:1 mixture of gg and gt conformers as is found in glucopyranose itself.

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Synthesis of (6R)- and (6S)-d-Glucose-6-²H through Stereospecific Photo-bromination of 1,6-Anhydro-β-d-glucopyranose Derivative

Cited by 7 publications

References 3 publications

Interplay of Protecting Groups and Side Chain Conformation in Glycopyranosides. Modulation of the Influence of Remote Substituents on Glycosylation?

Interplay of Protecting Groups and Side Chain Conformation in Glycopyranosides. Modulation of the Influence of Remote Substituents on Glycosylation?

Intramolecular deuterium distributions reveal disequilibrium of chloroplast phosphoglucose isomerase

Stereospecific synthesis of methyl 2-amino-2-deoxy-(6S)-deuterio-α,β-d-glucopyranoside and methyl 2,6-diamino-2,6-dideoxy-(6R)-deuterio-α,β-d-glucopyranoside: Side chain conformations of the 2-amino-2-deoxy and 2,6-diamino-2,6-dideoxyglucopyranosides

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Synthesis of (6R)- and (6S)-d-Glucose-6-2H through Stereospecific Photo-bromination of 1,6-Anhydro-β-d-glucopyranose Derivative

Cited by 7 publications

References 3 publications

Interplay of Protecting Groups and Side Chain Conformation in Glycopyranosides. Modulation of the Influence of Remote Substituents on Glycosylation?

Interplay of Protecting Groups and Side Chain Conformation in Glycopyranosides. Modulation of the Influence of Remote Substituents on Glycosylation?

Intramolecular deuterium distributions reveal disequilibrium of chloroplast phosphoglucose isomerase

Stereospecific synthesis of methyl 2-amino-2-deoxy-(6S)-deuterio-α,β-d-glucopyranoside and methyl 2,6-diamino-2,6-dideoxy-(6R)-deuterio-α,β-d-glucopyranoside: Side chain conformations of the 2-amino-2-deoxy and 2,6-diamino-2,6-dideoxyglucopyranosides

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Synthesis of (6R)- and (6S)-d-Glucose-6-²H through Stereospecific Photo-bromination of 1,6-Anhydro-β-d-glucopyranose Derivative