Cyclic Hexapeptides with Free Carboxylate Groups as New Receptors for Monosaccharides

Abstract

[structure: see text]. Cyclic hexapeptides composed of alternating L-proline and 3-aminobenzoic acid subunits with substituents on the aromatic subunits that contain free carboxylate groups are able to bind monosaccharides in 4% CD3OD/CDCl3. The binding selectivity of these peptides depends on the structure of the substituents on the aromatic subunits.

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

“…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)(2)(3)(4)(5)(6)(7)(8)(9)(10)(11)(12)(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)(15)(16)(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)(4)(5)(6). In the presence of liquid water, the problem becomes yet more difficult.…”

Synthesis and duplex formation of the reverse amidohelicene tetramer

“…1,3,5-Benzenetricarboxylate with three differentiated carboxylates was synthesized. 10 Monosodium salt of 1,3,5-benzenetricarboxylic acid 10 was reacted with 1-bromodecane in DMF at room temperature giving decyl ester 11 in 37% yield. The treatment of 11 sodium salt with benzyl bromide gave decyl benzyl ester 12 in 52% yield.…”

Bicyclic Organo‐Peptides as Selective Carbohydrate Receptors: Design, Solid‐phase Synthesis, and on‐bead Binding Capability

“…Most of them contain specific recognition motifs, such as hydrogen bond donor or acceptor systems (amides [9b, 9c, 13], (thio)ureas [14], or phosphates [15]). However, to our knowledge, there are few examples of peptide-derived receptors for selective carbohydrate recognition [16], although amino acids are the constituents of natural protein binding pockets, and amide as recognition motif is among the most pronounced feature in above reported cases. This lack is rather surprising since the use of peptide-derived receptors has already turned out to be successful in the discovery of selective receptors for cations like iron [17], anions including sulfate [18] and chloride [19], amino acids [20], and even peptides [21] or ATP and GTP nucleotides [22].…”

“…HPLC: t R 6.9 min; HR-ES-MS: calcd (M H C 41 H 66 N 13 O 15 ), 980.4803; found, m/z 980.4708. N-(9H-Fluoren-9-ylmethoxycarbonyl)-l-S-(benzyl)cystei nyl-l-alanine tert-butyl ester (16). A solution of 15 (130 mg, 0.24 mmol), DIPEA (124 mL, 3 eq) and benzyl bromide (120 mL, 3 eq) in DMF (5 mL) was stirred at r. t. for 1 h. Then the solvent was evaporated under reduced pressure and the residue purified by column chromatography (1 : 2 EtOAc-Petroleum ether) to furnish 16 in 89% .…”