Synthesis of aryl-thioglycopeptides through chemoselective Pd-mediated conjugation† †Electronic supplementary information (ESI) available: General, experimental procedures, and characterization of all new compounds. See DOI: 10.1039/c8sc02370k

• Published in: Chemical science (Cambridge) Vol. 9; no. 46; pp. 8753 - 8759
• Main Authors: Montoir, David, Amoura, Mehdi, Ababsa, Zine El Abidine, Vishwanatha, T. M., Yen-Pon, Expédite, Robert, Vincent, Beltramo, Massimiliano, Piller, Véronique, Alami, Mouad, Aucagne, Vincent, Messaoudi, Samir
• Format: Journal Article
• Language: English
• Published: Royal Society of Chemistry 20-09-2018
• Subjects: Chemistry
• ISSN: 2041-6520; 2041-6539
• DOI: 10.1039/c8sc02370k

A highly chemoselective thioglycoconjugation method of iodoaryl aminoacids, small peptides and complex unprotected polypeptides is reported.
We describe herein a Pd-catalyzed methodology for the thioglycoconjugation of iodoaryl peptides and aminoacids. This operationally simple process occurs under semi-aqueous conditions and displays wide substrate scope. The strategy has been successfully applied to both the thioglycosylation of unprotected peptides and the generation of thioglyco-aminoacid building blocks, including those suitable for solid phase peptide synthesis. To demonstrate the broad potential of this technique for late stage functionalization, we successfully incorporated challenging unprotected β-
S
-GlcNAc- and α-
S
-GalNAc-derivatives into very long unprotected peptides. This study opens the way to new applications in chemical biology, considering the well-recognized advantages of
S
-glycosides over
O
-glycosides in terms of resistance towards both enzymatic and chemical degradation.