Synthese von Glycopeptiden und Lipopeptiden durch chemoselektive Verknüpfung

Abstract

Vollständig ungeschützte Peptide mit chemoselektiv zugänglichen Gruppen reagieren unter sehr milden Bedingungen mit freien reduzierenden Zuckern oder Lipidaldehyden. Damit ergibt sich ein einfacher Zugang zu komplexen Glycopeptiden wie 1, einem Somatostatin‐Analogon, und Lipopeptiden.

Molecular Design of Glycoprotein Mimetics: Glycoblotting by Engineered Proteins with an Oxylamino‐Functionalized Amino Acid Residue

“…[13,14] Recently, it was also reported that combined use of the glycoblotting by oxylamino-containing polymers and MALDI-TOF/TOF mass spectrometry allows for both facile purification and precise analysis of common oligosaccharides and glycopeptides from human serum or mouse skin glycoproteins. [11,15] In this study, two unnatural amino acids, 2-amino-4-O-(N-methylaminooxy) butanoic acid (1) and 2-amino-4-aminooxy butanoic acid (2), were employed for the synthesis of novel aminoacyl-tRNA (Figure 1).…”

“…N-Methyl-N-tert-butoxycarbonylhydroxylamine (86 mg, 0.27 mmol) was added to the solution, and the mixture was stirred at 0 8C for 1 h. To the mixture was added ice water and the mixture was extracted with ethyl acetate. 28 (m, 2 H, b-H 2 ), 1.46 (s, 9 H, (CH 3 ) 3 -C-); 13 , detection at 260 nm), the products with the retention time of 14.2 and 14.5 min were collected as the two positional (2',3') isomers. After 2 h, Et 2 O (1 mL) was added to the solution and then the precipitation was collected by a centrifugation (20 000 g, 4 8C, 5 min).…”

“…1 H and 13 C NMR spectra were recorded and measured at 600 and 120 MHz, respectively, with AVANCE 600 (Bruker) using CDCl 3 as a solvent. All signals of the new compounds synthesized in this study were characterized with H,H COSY and HMQC techniques.…”

Chemoselective Capture of Glycans for Analysis on Gold Nanoparticles: Carbohydrate Oxime Tautomers Provide Functional Recognition by Proteins

“…[1][2][3] Solid-phase chemical methods are gaining importance as a tool enabling the study of these processes. [4] Chemoselective coupling of unprotected carbohydrates to, for example, polymeric supports, [5][6][7] microarrays, [8][9][10] peptides and proteins, [11] and to other surfaces [12] through oxime formation has been widely exploited in recent years as a means to capture glycans from natural sources and to obviate laborious glycosylation and protecting-group chemistry. The reaction exploits the unique availability of an aldehyde moiety in the reducing-end of glycans, which also allows, for example, reductive amination, hydrazone and acyl hydrazone formation, and thiazolidine formation.…”

Versatile Glycoblotting Nanoparticles for High‐Throughput Protein Glycomics

“…[7] Mutter reported that aminooxyl groups are also reactive with the hemiacetal of the carbohydrate through a stable oxime bond. [8] Herein, we present an effective and practical trapand-release method based on chemoselective ligation of carbohydrates with oxylamino groups attached to the surface of nanoparticles ( Figure 1) and describe the optimal conditions for glycoblotting and the versatility of this method. We have chosen an oxylamine-functionalized photopolymerizable lipid as an anchor molecule for capturing oligosaccharides.…”