Late-stage C(sp²)–H and C(sp³)–H glycosylation of <i>C</i>-aryl/alkyl glycopeptides: mechanistic insights and fluorescence labeling

Abstract

C(sp³)-H and C(sp²)-H glycosylations of structurally complex amino acids and peptides were accomplished through the assistance of triazole peptide-isosteres. The palladium-catalyzed peptide-saccharide conjugation provided modular access to structurally complex <i>C</i>-alkyl glycoamino acids, glycopeptides and <i>C</i>-aryl glycosides, while enabling the assembly of fluorescent-labeled glycoamino acids. The C-H activation approach represents an expedient and efficient strategy for peptide late-stage diversification in a programmable as well as chemo-, regio-, and diastereo-selective fashion.