Constitution of Two Aldobiouronic Acids from Wheat Bran Hemicellulose<sup>1,2</sup>

Adams, G. A.; Bishop, C. T.

doi:10.1021/ja01593a054

Cited by 23 publications

(7 citation statements)

References 2 publications

(3 reference statements)

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“…l - gluco -Heptenitol 8b (18 mg, 0.101 mmol) was subjected to ozonolysis (general method 1) to give l -glucose 11 as colorless oil (16 mg, 88%): R f 0.12 (CHCl 3 /MeOH/H 2 O 14:6:1); [α] D 25 −33 ( c 1.0, H 2 O, 18h), lit. 37 ( d -glucose) + 50.1 ( c 0.7, H 2 O); Spectral data in accordance with a commercially sample of d -glucose (see Supporting Information ).…”

Section: Experimental Sectionmentioning

confidence: 66%

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Indium- and Zinc-Mediated Acyloxyallylation of Protected and Unprotected Aldotetroses—Revealing a Pronounced Diastereodivergence and a Fundamental Difference in the Performance of the Mediating Metal

et al. 2018

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The acyloxyallylation of unprotected aldoses was first demonstrated more than a decade ago as a potentially elegant two-carbon homologation of reducing sugars (upon ozonolysis); however, its application in real case syntheses remained scarce. Following up on such a successful showcase and to answer several pending questions about this attractive transformation, we engaged in an in depth methodological reinvestigation. The epimeric tetroses l-erythrose and d-threose in unprotected and protected form were successfully applied to the indium and also zinc-mediated acyloxyallylation, with the latter being a first for an unprotected sugar. The investigation largely benefited from the choice of these more exotic starting materials as it allowed unambiguous identification/quantification of the hexose-products which are available as authentic reference materials. The observed diastereoselectivities indicate a strong substrate control (stereochemistry at O2), and the influence of the reagent’s structure on the selectivity was investigated in great detail. A strong facial diastereodivergence between related protected and unprotected structures was demonstrated and an unexpected, pronounced principle difference in performance between indium and zinc was revealed.

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Section: Experimental Sectionmentioning

confidence: 66%

Section: Experimental Sectionmentioning

confidence: 99%

Indium- and Zinc-Mediated Acyloxyallylation of Protected and Unprotected Aldotetroses—Revealing a Pronounced Diastereodivergence and a Fundamental Difference in the Performance of the Mediating Metal

et al. 2018

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“…The 4-0-methylglucuronosylxylose from oat coleoptiles also behaved identically, in solvents (a) and (b) (see Experimental section), with an authentic sample of 2-0-(4-0-methyl-OC-D-glucopyranosyluronic acid)-D-xylose kindly supplied by C. T. Bishop (see Adams & Bishop, 1956).…”

Section: Resultsmentioning

confidence: 83%

Uronic acid constituents of oat-coleoptile cell walls

Ray¹,

Rottenberg²

1964

Biochemical Journal

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“…I t was pointed out in an earlier publication (25) that the presence of a methyl ether substitueilt on C(4) of the glucuronic acid is associated with glycosidic attachment to C(?, of the xylose unit. Recently Brasch and Wise have isolated 3-0-cr-(4-0-methyl-~-g l~~~r o n~~y l ) -D -~y l~~e from Monterey pine (13) and have suggested that it may be a component of other woods; however, careful examination of the hydrolyzate from white spruce has not revealed the presence of this component.…”

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confidence: 99%

Uronic Acids From White Spruce (Picea Glauca (Moench) Voss)

Adams¹

1959

Can. J. Chem.

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Acid hydrolysis of extractive-free white spruce wood produced a nilmber of neutral and acidic sugars and oligosaccharides. The acidic components were isolated and three of these were shown to be 4-O-methyl-~-gluc~1ronic acid, 2-0-(4-0-methyl-a-D-glucopyranosyluronic acid)-D-xylose, and tentatively 0-(~-0-nlethy~-a-~-g~ucopyranosy~~1ronic acid)-Investigations of the hemicelluloses 01 white spruce (Picea glauca) have yielded an arabogalactan (1) and a glucomannan (2). Since neither of these fractions contained more than a trace of uronic acids, it seemed likely that the acid components were associated with the xylan portion of the wood. The present communication is concerned with the composition and ideiltification of three uronic acid components isolated from spruce wood by partial hydrolysis.The uronic acids were obtained by acid hydrolysis of extractive-free white spruce wood and separated from the neutral sugars by adsorption on an anion exchange resin. Further separation of the recovered uronic acid components yielded several fractions of which three (I, 11, and 111) were identified.Chromatographic evidence, methoxyl content, and equivalent weight tentatively identified fraction I as 4-0-methyl-D-glucuronic acid. Conversion of the acid to its methyl ester methyl glycoside and reduction with lithium aluminum hydride yieldecl 4-O-methyl-~-gl~1cose, which was characterized as crystalline 4-0-methyl-D-glucose phenylosazone.Hydrolysis of fraction I1 and chromatographic examination of the hydrolyzate indicated the presence of D-xyloSe and 4-0-methyl-D-glucuronic acid. Reduction of the ester glycosicle gave the corresponding disaccharide glycoside which on hydrolysis yieldecl crystalline D-xyloSe and 4-0-methyl-D-glucose, the latter being identified as its crystalline phenylosazone. The point of attachment of the 4-O-methyl-~-glucuronic acid to the D-xyloSe residue was determined by methylation studies. The aldobiouronic acid methyl ester, methyl glycoside, was converted to methyl-0-(4-0-methyl-D-glucopyranosy1)-D-xyloside by reduction with lithium aluminum hydride and the product was then fully methylated. On hydrolysis it yieldecl 3,4-di-0-methyl-D-xylose and 2,3,4,6-tetra-0-methyl-D-glucose thus proving that the acid was attached glycosidically to C(?, of the xylose residue. Recent evidence has established that the glycosidic bond in this alclobiouronic acid is in the a configuration (3). These findings showed that the aldobiouronic acid was 2-0-(4-0-methyl-a-~-glucopyranosfiroi1c acid)-D-xylopyranose.The aldotriouronic acid (fraction 111) nras composed of 4-0-methyl-D-glucuronic acid and D-xyloSe and had [a]: + 5 g 0 . I t could not be obtained in crystalline form. The attachment of the 4-0-methyl-D-glucuronic acid and the xylose units to one another was determined by methylation studies. The aldotriouronic acid was converted to its corresponding methyl ester methyl glycoside by treatment with 1% methanolic hydrogen chloride a t room temperature. Reduction with lithium alumiilum hydride provided the

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Constitution of Two Aldobiouronic Acids from Wheat Bran Hemicellulose^1,2

Cited by 23 publications

References 2 publications

Indium- and Zinc-Mediated Acyloxyallylation of Protected and Unprotected Aldotetroses—Revealing a Pronounced Diastereodivergence and a Fundamental Difference in the Performance of the Mediating Metal

Indium- and Zinc-Mediated Acyloxyallylation of Protected and Unprotected Aldotetroses—Revealing a Pronounced Diastereodivergence and a Fundamental Difference in the Performance of the Mediating Metal

Uronic acid constituents of oat-coleoptile cell walls

Uronic Acids From White Spruce (Picea Glauca (Moench) Voss)

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Constitution of Two Aldobiouronic Acids from Wheat Bran Hemicellulose1,2

Cited by 23 publications

References 2 publications

Indium- and Zinc-Mediated Acyloxyallylation of Protected and Unprotected Aldotetroses—Revealing a Pronounced Diastereodivergence and a Fundamental Difference in the Performance of the Mediating Metal

Indium- and Zinc-Mediated Acyloxyallylation of Protected and Unprotected Aldotetroses—Revealing a Pronounced Diastereodivergence and a Fundamental Difference in the Performance of the Mediating Metal

Uronic acid constituents of oat-coleoptile cell walls

Uronic Acids From White Spruce (Picea Glauca (Moench) Voss)

Contact Info

Product

Resources

About

Constitution of Two Aldobiouronic Acids from Wheat Bran Hemicellulose^1,2