A Tricyclic Polyamide Receptor for Carbohydrates in Organic Media

Davis, Anthony P.; Wareham, Richard S.

doi:10.1002/(sici)1521-3773(19980904)37:16<2270::aid-anie2270>3.3.co;2-y

Cited by 20 publications

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“…The central framework was constructed although two [2 ϩ 2] macrocyclizations, the first to yield 13 and the second to yield the final product. These reactions could be accomplished in acceptable yield at high dilution, because the resulting 24-membered rings are the smallest possible without unreasonable strain (25). Key intermediates were the biphenyl component 7 (25), and the new isophthaloyl spacer unit 12.…”

Section: Resultsmentioning

confidence: 99%

“…These reactions could be accomplished in acceptable yield at high dilution, because the resulting 24-membered rings are the smallest possible without unreasonable strain (25). Key intermediates were the biphenyl component 7 (25), and the new isophthaloyl spacer unit 12. To enable the sequential cyclizations, orthogonal protecting groups were used at either end of 7.…”

Section: Resultsmentioning

confidence: 99%

“…¶ See ref. 25 for a related control experiment, involving a monocyclic analogue of 1a. In this case 1 H NMR titration revealed a much reduced affinity for glucoside 14a in CDCl3.…”

Section: Resultsmentioning

confidence: 99%

“…The order of extractabilities (glucose Ͼ galactose Ͼ mannose) does not reflect the estimated degrees of hydration (mannose Ͻ glucose Ͻ galactose) (32,33), suggesting a stereospecific interaction with the receptor. Indeed, as initially proposed (25), the tricyclic core of 1 may be especially complementary to substrates with equatorial substituents. In this context, it is notable that xylose 20 is also strongly extracted.…”

Section: H Nmrmentioning

confidence: 99%

“…§ Recently we described the tricyclic tetraester 1a (Fig. 1), a novel receptor that showed an exceptional affinity for n-octyl ␤-D-glucoside, remarkable ␤ vs. ␣ selectivity, and the unusual ability to dissolve solid glucose in CHCl 3 (25). Although we hoped to demonstrate the extraction of glucose from aqueous solution by using 1a, our attempts were frustrated by solubility problems.…”

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Phase transfer of monosaccharides through noncovalent interactions: Selective extraction of glucose by a lipophilic cage receptor

Ryan

Lecollinet²,

Velasco³

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

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We have previously shown that macrotricyclic host 1a is a powerful receptor for glucopyranosyl units in the nonpolar medium of chloroform. However, the solubility properties of 1a did not permit studies of the extraction of carbohydrates from aqueous solution. This paper describes the synthesis of the new variant 1b, furnished with a highly lipophilic exterior array of 12 benzyloxy substituents. In homogeneous solution, 1b behaves much as 1a, binding n-octyl ␤-D-glucoside with Ka ‫؍‬ 720 M ؊1 in CD3OH͞CDCl3 (8:92). In twophase experiments, the improved solubility of 1b allows carbohydrate extraction to be observed. Three hexoses (glucose, galactose, and mannose), two pentoses (ribose and xylose), and the two methyl glucosides are all extracted substantially into chloroform from 1 M aqueous solutions. Among the hexoses, 1b shows notable affinity and selectivity for glucose, extracting detectable amounts even from 0.1 M aqueous solutions. C arbohydrate recognition is an active area of supramolecular chemistry, motivated by the biological importance of saccharides and also by the unusual challenge represented by these complex substrates (1-13). On the one hand, carbohydrates must be recognized and processed during metabolism, whereas saccharide motifs are known to mediate cell-cell recognition, the infection of cells by pathogens, and many aspects of the immune response (14-17). On the other, carbohydrates possess structures that are fairly large, irregular, and multivalent, while being quite similar to clusters of water molecules. Even in nonpolar solvents, selective carbohydrate receptors require extended, sophisticated architectures (1, 3-6). In the presence of liquid water, the problem becomes yet more difficult. Recognition by means of boronate formation has been relatively successful (2, 7-10), but there are few effective systems for binding saccharides from water by using noncovalent bonds (1, 11-13).A receptor can be shown to discriminate between saccharide and water in one of two ways. Firstly (and most obviously), it can be studied in homogeneous aqueous solution. Secondly, it can be designed for solubility in nonpolar media and studied in a two-phase system, demonstrating the ability to extract or transport the carbohydrate (18)(19)(20)(21)(22)(23)(24). This latter approach is directly relevant to the transport of carbohydrates across biological membranes. Boron-based systems have again proved quite effective (22-24). However, for those receptors operating through noncovalent interactions, success has been limited thus far. Positive results have been obtained with the less hydrophilic saccharides at high aqueous concentrations (18, 20), but not in general with the more hydrophilic substrates such as glucose. § Recently we described the tricyclic tetraester 1a (Fig. 1), a novel receptor that showed an exceptional affinity for n-octyl ␤-D-glucoside, remarkable ␤ vs. ␣ selectivity, and the unusual ability to dissolve solid glucose in CHCl 3 (25). Although we hoped to demonstrate the extraction of glucose ...

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

“…¶ See ref. 25 for a related control experiment, involving a monocyclic analogue of 1a. In this case 1 H NMR titration revealed a much reduced affinity for glucoside 14a in CDCl3.…”

Section: Resultsmentioning

confidence: 99%

Section: H Nmrmentioning

confidence: 99%

mentioning

confidence: 99%

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Phase transfer of monosaccharides through noncovalent interactions: Selective extraction of glucose by a lipophilic cage receptor

Ryan

Lecollinet²,

Velasco³

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

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A Synthetic Galectin Mimic

et al. 2021

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Galectins are a galactoside specific subclass of carbohydrate binding proteins (lectins) involved in various cellular activities, certain cancers, infections, inflammations, and many other biological processes. The molecular basis for the selectivity of galectins is well‐documented and revolves around appropriate interaction complementarity: an aromatic residue for C−H⋅⋅⋅π interactions and polar residues for (charge assisted) hydrogen bonds with the axial hydroxyl group of a galactoside. However, no synthetic mimics are currently available. We now report on the design and synthesis of the first galectin mimic (6), and show that it has a higher than 65‐fold preference for n‐octyl‐β‐galactoside (8) over n‐octyl‐β‐glucoside (7) in CD2Cl2 containing 5 % [D6]DMSO (with Ka≥4500 M−1 for 6:8). Molecular modeling informed by nOe studies reveal a high degree of interaction complementarity between 6 and galactoside 8, which is very similar to the interaction complementarity found in natural galectins.

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Recent progress of chiral stationary phases for separation of enantiomers in gas chromatography

Xie

Yuan

2016

J of Separation Science

104

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Chromatography techniques based on chiral stationary phases are widely used for the separation of enantiomers. In particular, gas chromatography has developed rapidly in recent years due to its merits such as fast analysis speed, lower consumption of stationary phases and analytes, higher column efficiency, making it a better choice for chiral separation in diverse industries. This article summarizes recent progress of novel chiral stationary phases based on cyclofructan derivatives and chiral porous materials including chiral metal-organic frameworks, chiral porous organic frameworks, chiral inorganic mesoporous materials, and chiral porous organic cages in gas chromatography, covering original research papers published since 2010. The chiral recognition properties and mechanisms of separation toward enantiomers are also introduced.

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A Tricyclic Polyamide Receptor for Carbohydrates in Organic Media

Cited by 20 publications

References 0 publications

Phase transfer of monosaccharides through noncovalent interactions: Selective extraction of glucose by a lipophilic cage receptor

Phase transfer of monosaccharides through noncovalent interactions: Selective extraction of glucose by a lipophilic cage receptor

A Synthetic Galectin Mimic

Recent progress of chiral stationary phases for separation of enantiomers in gas chromatography

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