title: Orthogonal dual thiol-chloroacetyl and thiol-ene couplings for the sequential one-pot assembly of heteroglycoclusters.
abstract: We describe the first one-pot orthogonal strategy to prepare well-defined cyclopeptide-based heteroglycoclusters (hGCs) from glycosyl thiols. Both thiol-chloroactetyl coupling (TCC) and thiol-ene coupling (TEC) have been used to decorate cyclopeptides regioselectively with diverse combination of sugars. We demonstrate that the reaction sequence starting with TCC can be performed one-pot whereas the reverse sequence requires a purification step after the TEC reaction. The versatility of this orthogonal strategy has been demonstrated through the synthesis of diverse hGCs displaying alternating binary combinations of α-D-Man or β-D-GlcNAc, thus providing rapid access to attractive heteroglycosylated platforms for diverse biological applications.
authors.affiliation: Département de Chimie Moléculaire, UMR-CNRS 5250 & ICMG FR2607, Université Joseph Fourier, PB 53, 38041 Grenoble Cedex 9, France.
authors.forename: Michele
authors.initials: M
authors.lastname: Fiore
authors.affiliation: Département de Chimie Moléculaire, UMR-CNRS 5250 & ICMG FR2607, Université Joseph Fourier, PB 53, 38041 Grenoble Cedex 9, France.
authors.forename: Gour Chand
authors.initials: GC
authors.lastname: Daskhan
authors.affiliation: Département de Chimie Moléculaire, UMR-CNRS 5250 & ICMG FR2607, Université Joseph Fourier, PB 53, 38041 Grenoble Cedex 9, France.
authors.forename: Baptiste
authors.initials: B
authors.lastname: Thomas
authors.affiliation: Département de Chimie Moléculaire, UMR-CNRS 5250 & ICMG FR2607, Université Joseph Fourier, PB 53, 38041 Grenoble Cedex 9, France ; Institut Universitaire de France, 103 Boulevard Saint-Michel, 75005 Paris, France.
authors.forename: Olivier
authors.initials: O
authors.lastname: Renaudet
keywords: chemoselective ligation; heteroglycocluster; multivalency; multivalent glycosystems; one-pot synthesis