Synthesis of Some Iodo-sugar Derivatives<sup>1</sup>

The structural requirements for binding to the glucose/sorbose-transport system in the human erythrocyte were explored by measuring the inhibition constants, K(i), for specifically substituted analogues of d-glucose when l-sorbose was the penetrating sugar. Derivatives in which a hydroxyl group in the d-gluco configuration was inverted, or replaced by a hydrogen atom, at C-1, C-2, C-3, C-4 or C-6 of the d-glucose molecule, all bound to the carrier, confirming that no single hydroxyl group is essential for binding to the carrier. The binding and transport of 1-deoxy-d-glucose confirmed that the sugars bind in the pyranose form. The relative inhibition constants of d-glucose and its deoxy, epimeric and fluorinated analogues are consistent with the combination of beta-d-glucopyranose with the carrier by hydrogen bonds at C-1, C-3, probably C-4, and possibly C-6 of the sugar. Both polar and non-polar substituents at C-6 enhance the affinity of d-glucose derivatives relative to d-xylose, and d-galactose derivatives relative to l-arabinose, and it is suggested that the carrier region around C-6 of the sugar may contain both hydrophobic and polar binding groups. The spatial requirements at C-1, C-2, C-3, C-4 and C-6 were explored by comparing the relative binding of d-glucose and its halogeno and O-alkyl substituents. The carrier protein closely approaches the sugar except at C-3 in the d-gluco configuration, C-4 and C-6. d-Glucal was a good inhibitor, showing that a strict chair form is not essential for binding. 3-O-(2',3'-Epoxypropyl)-d-glucose, a potential substrate-directed alkylating agent, bound to the carrier, but did not inactivate it.

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“…156°C (Taylor & Kent, 1958); 6-deoxy-6-iodo-D-galactose, m.p. 1°C (Raymond & Schroeder, 1948); D-allose, m.p. 141-142°C (Sowa & Thomas, 1966).…”

Section: Materials and Methods Materialsmentioning

confidence: 99%

Structural requirements for binding to the sugar-transport system of the human erythrocyte

Barnett

Holman

Munday

1973

Biochemical Journal

226

147

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“…Eine Losung von 2,GO g (10 mmol) 1,2; 3,4-Di-O-isopropyliden-a-D-galactopyranose [30] in 40 ml Benzen wird rnit 17 m l 2 n Natronlauge und 0,28 g (0,s mmol) Tetra-n-butylammoniumbromid versetzt. Untcr kraftigem Riihren IaBt man bei 5--10°C innerhalb von 2 h eine Losung von 6,40 g (40 mmol) KMnO (50 mmol) Diphenyldiazomethan [29] umgesetzt und aufgearbeitet.…”

Section: 2;34-di-o-isopropyliden-a-d-galactopyranurons~ure (1)unclassified

Galacturonsäurederivate. I. Galacturonate aus Acetyl‐ und Isopropyliden‐D‐galactopyranosen

1990

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Galacturonic Acid Derivatives. I. Galacturonates from Acetyl‐ and Isopropylidene‐D‐galactopyranoses Galacturonic acid derivatives to be employed as glycosyl donors in saccharide synthesis are prepared from galacturonic acid itself or from galactose. Various syntheses of 1,2,3,4‐tetra‐O‐acetyl‐D‐galactopyranuronic acids (6) with differently protected carboxyl group and attempts of their conversion into galacturonpyranosyl bromides are described. The starting materials were 1,2;3,4‐di‐O‐isopropylidene‐α‐D‐galactopyranose and acetylated galactopyranose derivatives, respectively.

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“…(4). A mixture containing 3 (2 g, 6.5 mmol) [22], Ac20 (10 ml) and Py (15 ml) was stirred at r.t. for 3 h. Evaporation gave a residue, which was crystallized from EtOH to afford 2.74 g (97%) of 4 as white needles, identical with an authentic sample [38]. (5).…”

Section: Experimental Partmentioning

confidence: 97%

Synthesis of a Glyoxalase I Inhibitor from Streptomyces griseosporeus NIIDAet OGASAWARA

Mirza

Molleyres

Vasella

1985

Helvetica Chimica Acta

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The pseudolactones 6 and 12 were prepared in a straightforward way from methyl α‐D‐glucopyranoside and methyl α‐D‐mannopyranoside, respectively. The pseudolactone 6 reacted with tert‐butyl lithioacetate to give the protected, trihydroxylated cyclohexenone carboxylate 7 (51 %). The sterically hindered, L‐ribo‐configurated pseudolactone 12 reacted with diethyl ethylphosphonate and dimethyl methylphosphonate to give the protected trihydroxycyclohexenones 17 (49 %) and 18 (62 %), respectively. The hydroxymethylated cyclohexenone 21 was obtained from 18 by treatment with Me2AlSPh and then formaldehyde, oxidation of the product 19, and elimination. Deprotection of 21 gave 2, identical with KD16‐Ul. Esterification of 2 gave 1, identical with the title compound. Alternatively, 1 was obtained in higher yields by esterification of 21, followed by deprotection of the hydroxy groups. This synthesis gave 1 and 2 from methyl α‐D‐mannopyranoside in an overall yield of 18 and 20 %, respectively, confirming their absolute configuration.

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Synthesis of Some Iodo-sugar Derivatives¹

Cited by 75 publications

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Structural requirements for binding to the sugar-transport system of the human erythrocyte

Structural requirements for binding to the sugar-transport system of the human erythrocyte

Galacturonsäurederivate. I. Galacturonate aus Acetyl‐ und Isopropyliden‐D‐galactopyranosen

Synthesis of a Glyoxalase I Inhibitor from Streptomyces griseosporeus NIIDAet OGASAWARA

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Synthesis of Some Iodo-sugar Derivatives1

Cited by 75 publications

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Structural requirements for binding to the sugar-transport system of the human erythrocyte

Structural requirements for binding to the sugar-transport system of the human erythrocyte

Galacturonsäurederivate. I. Galacturonate aus Acetyl‐ und Isopropyliden‐D‐galactopyranosen

Synthesis of a Glyoxalase I Inhibitor from Streptomyces griseosporeus NIIDAet OGASAWARA

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Synthesis of Some Iodo-sugar Derivatives¹