Carboxymethylglycoside lactones (CMGLs): structural variations on the carbohydrate moiety

A practical and robust synthetic method to obtain the natural disaccharide sambubiose (2-O-β-D-xylopyranosyl-D-glucopyranose) is reported, exploring the key step in the synthesis, i.e., stereoselective O-glycosylation. Specifically, the best combinations of glycoside donors and acceptors were identified, stereospecific control of the reaction was achieved by screening several catalysts and protection/deprotection steps were evaluated and improved. The best result was obtained by coupling allyl 3,5,6-tri-O-benzyl-β-D-glucofuranoside with 2,3,4-tri-O-acetyl-D-xylopiranosyl-α-trichloro acetimidate in the presence of trimethylsilyl triflate as a catalyst giving the corresponding protected target compound as a correct single isomer. The latter was transformed accordingly into the desired final product by deprotection steps (deallylation, deacetylation, and debenzylation). Sambubiose was synthesized into a satisfactory and higher overall yield than previously reported and was also characterized.

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“…[α] 20 D = +19.5 (c 0.2, CHCl 3 ). The physico-chemical data are in agreement with those reported in the literature [ 28 ].…”

Section: Methodssupporting

confidence: 90%

Total Synthesis of Natural Disaccharide Sambubiose

et al. 2020

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“…Bicyclic systems like carboxymethylglycoside lactones (CMGLs) prepared from isomaltulose [227][228] or from the oxidation of corresponding allyl glycosides [229] provide amphiphilic amides by treatment with fatty amines in anhydrous CH 2 Cl 2 . Let us note that further functionalization of glucamides can be performed, such as in the case of sulfated urnoamides [230,231].…”

Section: From Carbohydrate Acids and Lactonesmentioning

confidence: 99%

Carbohydrate-Based Amphiphiles: Resource for Bio-based Surfactants

Wang¹,

Queneau²

2018

Encyclopedia of Sustainability Science and Technology

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GLOSSARY Carbohydrates are a family of biomolecules, ubiquitous in Nature, based on a common polyhydoxylated backbone though varying in size (from small molecules to macromolecules), in fine structure (configuration and functionalization), and possessing a wide range of biological properties and roles making them indispensable to life. Amphiphiles are molecular architectures with parts exhibiting different types of polarity, generally including hydrophilic and hydrophobic groups. Surfactants are molecules possessing the ability to modulate interfacial tension, notably water surface tension. Bio-based chemicals are chemical products which are obtained by transformation of a starting material arising from biomass, such as carbohydrates, fats, proteins, terpenes. DEFINITION OF THE SUBJECT Surfactants are commodity chemicals used in an incredibly wide range of situations of the everyday life, and must therefore be improved constantly in terms of environmental impact, sustainability and performance. One way towards more sustainable surfactants is the use of renewable resources as raw materials for their manufacture, in place of fossil ones. Since the structure of surfactant combines a polar part to a hydrophobic one, carbohydrates, which are very polar molecules, appear as ideal candidates for serving as renewable building blocks in the synthesis of bio-based surfactants. Developed first with the aim of providing added-value to some agricultural crops and by products, this strategy shows nowadays a rebirth in the context of green and sustainable chemistry. The chapter illustrates, from the chemical point of view, the diversity of molecular structures which belong to the family of carbohydrate-based surfactants.

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“…The first one was based on the oxidative cleavage of the allyl glycoside double bond, and the second on the anomeric alkylation of partially or totally unprotected sugars with tert-butyl bromoacetate. A large family of mono-and disaccharidic lactones became available to us (Scheme 3) [3,4].…”

Section: Structural Variations: Extending the Cmgl Familymentioning

confidence: 99%

“…presence of 0.1 equiv of CUIP(EtO) 3 and NEt 3 . The evolution of 1 H NMR spectra is shown in Figure 1.…”

Section: Preliminary Exploration Of the Step Growth Polymerization Ofmentioning

confidence: 99%

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Carboxymethyl glycoside lactone (CMGL) synthons: Scope of the method and preliminary results on step growth polymerization of α-azide-ω-alkyne glycomonomers

et al. 2010

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Carboxymethyl glycoside lactones (CMGLs) are bicyclic synthons which open readily for accessing new types of pseudo-glycoconjugates, such as sugar-amino acid hybrids, neoglycolipids, pseudodisaccharides, and membrane imaging systems. After lactone opening, free OH-2 is available for further functionalization, leading to 1,2-bisfunctionalized derivatives. This strategy is illustrated herein with new polymerizable systems of the AB type bearing both azide and alkyne functions prepared from  or  gluco-CMGL synthons. After the reaction of lactones with propargylamine, an azido group was introduced by two different sequences leading to either the 2-manno-azido or the 6-gluco-azido products. The capability of these AB monomers to undergo step growth polymerization through copper(I) catalyzed alkyne-azide cycloaddition (CuAAC) and generate glycopolytriazoles was evidenced.

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Carboxymethylglycoside lactones (CMGLs): structural variations on the carbohydrate moiety

Cited by 17 publications

References 34 publications

Total Synthesis of Natural Disaccharide Sambubiose

Total Synthesis of Natural Disaccharide Sambubiose

Carbohydrate-Based Amphiphiles: Resource for Bio-based Surfactants

Carboxymethyl glycoside lactone (CMGL) synthons: Scope of the method and preliminary results on step growth polymerization of α-azide-ω-alkyne glycomonomers

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