<scp>d</scp>-Allose, a rare sugar. Synthesis of <scp>d</scp>-allopyranosyl acceptors from glucose, and their regioselectivity in glycosidation reactions

Vigo, Enrique A. Del; Stortz, Carlos A.; Marino, Carla

doi:10.1039/d2ob00590e

Cited by 5 publications

(3 citation statements)

References 55 publications

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“…Traditionally, these reactions are either performed on suitably protected monosaccharides (for an overview of the methods to synthesize allose using protecting groups, see a recent review) 8 or enzymatically. The use of enzymes in these epimerization reactions mostly requires the unprotected reducing sugars.…”

Section: Discussionmentioning

confidence: 99%

Site-Selective Modification of (Oligo)Saccharides

Witte

Minnaard

2022

ACS Catal.

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Oligosaccharides, either as such or as part of glycolipids, glycopeptides, or glycoproteins, are ubiquitous in nature and fulfill important roles in the living cell. Also in medicine and to some extent in materials, oligosaccharides play an important role. In order to study their function, modifying naturally occurring oligosaccharides, and building in reactive groups and reporter groups in oligosaccharides, are key strategies. The development of oligosaccharides as drugs, or vaccines, requires the introduction of subtle modifications in the structure of oligosaccharides to optimize efficacy and, in the case of antibiotics, circumvent bacterial resistance. Provided the natural oligosaccharide is available, site-selective modification is an attractive approach as total synthesis of the target is often very laborious. Researchers in catalysis areas, such as transition-metal catalysis, enzyme catalysis, organocatalysis, and photoredox catalysis, have made considerable progress in the development of site-selective and late-stage modification methods for mono- and oligosaccharides. It is foreseen that the fields of enzymatic modification of glycans and the chemical modification of (oligo)saccharides will approach and potentially meet each other, but there is a lot to learn and discover before this will be the case.

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Section: Discussionmentioning

confidence: 99%

Site-Selective Modification of (Oligo)Saccharides

Witte

Minnaard

2022

ACS Catal.

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“…Rare sugars are saccharides that exist in small quantities in nature and have attracted attention for their functions such as their ability to suppress postprandial blood glucose elevation [1,2]. Recently, enzymatic syntheses of monosaccharide rare sugars such as psicose and allose have been established [3][4][5], enabling their mass production and availability; it has also been reported that several rare sugars can be chemically synthesized via siteselective epimerization [6,7]. With this progress, novel oligosaccharides and glycosides derived from these monosaccharides and rare sugars by chemical synthesis could result in the creation of new functional food products.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Sucrose-Mimicking Disaccharide by Intramolecular Aglycone Delivery

Sano,

Ishiwata,

Takamori

et al. 2024

Molecules

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Rare sugars are known for their ability to suppress postprandial blood glucose levels. Therefore, oligosaccharides and disaccharides derived from rare sugars could potentially serve as functional sweeteners. A disaccharide [α-d-allopyranosyl-(1→2)-β-d-psicofuranoside] mimicking sucrose was synthesized from rare monosaccharides D-allose and D-psicose. Glycosylation using the intermolecular aglycon delivery (IAD) method was employed to selectively form 1,2-cis α-glycosidic linkages of the allopyranose residues. Moreover, β-selective psicofuranosylation was performed using a psicofuranosyl acceptor with 1,3,4,6-tetra-O-benzoyl groups. This is the first report on the synthesis of non-reducing disaccharides comprising only rare d-sugars by IAD using protected ketose as a unique acceptor; additionally, this approach is expected to be applicable to the synthesis of functional sweeteners.

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“…In general, an efficient enzymatic synthesis based on the Izumoring strategy has high specificity, which makes it environmentally friendly and sustainable, making it a highly favorable alternative to chemical synthesis for the preparation of d -allose. − l -Rhamnose isomerase (L-RI), which is responsible for the isomerization of d -allulose to d -allose, is the preferred biocatalyst for the synthesis of d -allose. − Several L-RIs have been identified and substantially investigated, but the studies largely concentrated on gene mining, strain screening, and enzymatic characterization . In all cases, the broader commercialization of these enzymes has been restricted by poor operational stability under harsh industrial reaction conditions.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Thermostability of an l-Rhamnose Isomerase for d-Allose Synthesis by Computation-Based Rational Redesign of Flexible Regions

Wei,

Gao,

Zhang

et al. 2023

J. Agric. Food Chem.

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D-Allose is a low-calorie rare sugar with great application potential in the food and pharmaceutical industries. The production of D-allose has been accomplished using L-rhamnose isomerase (L-RI), but concomitantly increasing the enzyme's stability and activity remains challenging. Here, we rationally engineered an L-RI from Clostridium stercorarium to enhance its stability by comprehensive computation-aided redesign of its flexible regions, which were successively identified using molecular dynamics simulations. The resulting combinatorial mutant M2-4 exhibited a 5.7-fold increased half-life at 75 °C while also exhibiting improved catalytic efficiency. Especially, by combining structure modeling and multiple sequence alignment, we identified an α0 region that was universal in the L-RI family and likely acted as a "helix-breaker". Truncating this region is crucial for improving the thermostability of related enzymes. Our work provides a significantly stable biocatalyst with potential for the industrial production of D-allose.

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d-Allose, a rare sugar. Synthesis of d-allopyranosyl acceptors from glucose, and their regioselectivity in glycosidation reactions

Abstract: Although D-allose (D-All) is a sugar with low natural abundance, it has a great pharmacological and alimentary potential due to its biological properties. However, its chemistry, regarding the regioselectivity in...

Cited by 5 publications

References 55 publications

Site-Selective Modification of (Oligo)Saccharides

Site-Selective Modification of (Oligo)Saccharides

Synthesis of Sucrose-Mimicking Disaccharide by Intramolecular Aglycone Delivery

Enhanced Thermostability of an l-Rhamnose Isomerase for d-Allose Synthesis by Computation-Based Rational Redesign of Flexible Regions

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