Chemoselective and site-selective peptide and native protein modification enabled by aldehyde auto-oxidation

We report a chemoselective and site-selective formylation of e-amine in native proteins. The aldehyde auto-oxidation re-routing, regulated generation of formate, and reversible N-terminus protection drive the transformation. It labels a single e-amine in a pool of its copies, other nucleophilic residues, and a-amine. The extension of the methodology leads to site-selective acylation.