Pyridyloxy-Directed, Pd(II)-Catalyzed Late-Stage C(sp²)–H Alkynylation and Olefination of Tyrosine Oligopeptides

Peptides and peptidomimetics have gained increasing interest as therapeutics due to their unique properties as small molecules and proteins. Herein, we report the pyridyloxy-directed Pd (II)-catalyzed C(sp²)-H alkynylation and olefination of tyrosine residues in peptides with high chemo- and site-selectivity. This method achieved the functionalization of tyrosine at any position of the amino acid for alkynylation and olefination. Furthermore, this approach can be used to synthesize peptide-biomolecule conjugates.