Single and dual glycoside clustering around calix[4]arene scaffolds via click thiol–ene coupling and azide–alkyne cycloaddition (original) (raw)
Related papers
Synthesis of upper rim calix[4]arene divalent glycoclusters via amide bond conjugation
Tetrahedron, 2005
Synthetic routes for linking two sugar units at the upper rim of cone calix[4]arenes, through the formation of amide bonds, have been explored. Steric effects prevent the coupling of calix[4]arene dicarboxylic acid with simple aminoglycosides, whereas the corresponding reaction with carbohydrates bearing a two or three carbon atoms spacer, terminating with a primary amino group, allows the synthesis of several difunctionalized calix[4]arene neoglycoconjugates, attractive in chemical glycobiology and supramolecular chemistry. q
Calix[8]arene-based glycoconjugates as multivalent carbohydrate-presenting systems
Tetrahedron Letters, 2003
An efficient approach for the introduction of eight mono-or disaccharide sugar moieties (D-glucose, N-acetyl-D-glucosamine, D-galactose, L-fucose, D-maltose and D-cellobiose) at the upper rim of calix[8]arene 1, using thioureido linkers, is reported. The obtained water-soluble, nanosized glycocalix[8]arenes 5b-10b may act as biomimetic carbohydrate systems and as hosts for highly polar organic molecules. Preliminary 1 H NMR complexation experiments of octaglycosyl derivative 7b and 10b with ionic guests are also reported.
Synthesis and Properties ofO-Glycosyl Calix[4]Arenes (Calixsugars)
Chemistry - A European Journal, 1997
Model 0-glycosylation reactions at either rim of calix arenes are described with the aim ofproviding access to 21 new family of carbohydrate-containing calixarene derivatives named calixsugars. One or two sugar moieties (u-mannofuranose and Li-glucopyranose) were introduced at the lower rim of the parent calix[4]arene by glycosylation of the phenolic hydroxyl groups by mcans of a Mitsunobu reaction. Tetrapropoxy calix[4]arcnes bearing two or four hydroxy-methyl groups at the upper rim wcre coupled with perbenzoylated thioethyl Dgalactoside and D-lactoside in thc presencc of the thiophilic promoter copper(i1) triflate. In this way /,'-linked bis-Keywords calixarenescarbohydrates * glycosylations host-guest chemistry * Mitsunobu reaction and tetrakis-0-galactosyl calix[4]arenes were obtained in good yield, the latter showing some solubility in water. For the 0-lactosyl derivatives only the bis-substituted compound could be obtained because of the competing formation of an intramolecular ether linkage between 1.3hydroxymethyl groups. Preliminary binding studies showed some affinity of the galactose-containing calixsugars toward charged carbohydrates and dihydrogen phosphate anion.
Synthesis of carbohydrate functionalised n-propoxy-Calix[4]arenes
Tetrahedron Letters, 1998
The Suzuki ~action has been used to couple para-bromophenyl glycosides to boronic acid derivatives ofn-propox3,-Calix[41arenc ; " a one-pot " methodology eliminates the need to isolate the boronic acids and increases the overall yield. The synthesis provides a new class of carbohydrate containing calixarencs with a deepened cavi .ly. In order to enlarge the cavity of calix[4]arene derivatives, Atwood et allhave prepared a pphenylcalix[4]arene tetramethylether. Such calix[4]arene derivative should be capable of binding organic guest molecules. However the methyl derivatives are present in the semi-cone conformation, which is neither optimised for guest binding nor for increasing carbohydrate recognition by cooperative interaction. 2 In view of this, the tetra-propyl derivatives blocked in the cone conformation are of great interest. Bearing in mind the significant role played by sugars in many biological events, the coupling of carbohydrate antennae to the calix[4]arenes may provide a new class of molecular vectors. To this end, Dondoni and Ungaro3'4et al have described the synthesis of calix[4]arenes substituted by carbohydrate units at
Organic Letters, 2004
the Mitsunobu protocol using the DEAD/TPP system. CA gave 1,3-dialkylated diols, while C 2 −C 10 glycols gave 1,2-and 1,3-bridged calixarenes. The reaction of TCA with C 2 diols afforded sulfonium phenoxide betaines via O,S-cyclization, which is the first example for the alkylation of the sulfide bridge.
Supramolecular Chemistry, 2008
HAL is a multidisciplinary open access archive for the deposit and dissemination of scientific research documents, whether they are published or not. The documents may come from teaching and research institutions in France or abroad, or from public or private research centers. L'archive ouverte pluridisciplinaire HAL, est destinée au dépôt et à la diffusion de documents scientifiques de niveau recherche, publiés ou non, émanant des établissements d'enseignement et de recherche français ou étrangers, des laboratoires publics ou privés.
Synthesis of Novel Calixsugars: Calix[4]arene–Monosaccharide Conjugates Based on Amide Bonds
Tetrahedron, 2000
Novel calix[4]arenes containing two sugar moieties in the molecule have been prepared. Both components are connected through the amidic bonds on the lower rim of a calixarene unit preorganised in the cone conformation. This design leads to new chiral receptors with potential recognition ability towards suitable guest molecules. ᭧ Scheme 1. (a) NaN 3 , DMF-H 2 O, NH 2 CONH 2 , 120ЊC, two days; (b) PPh 3 , THF, rt.