Chemoselective synthesis and analysis of naturally occurring phosphorylated cysteine peptides.

ABSTRACT: In contrast to protein O-phosphorylation, studying the function of the less frequent N- and S-phosphorylation events have lagged behind because they have chemical features that prevent their manipulation through standard synthetic and analytical methods. Here we report on the development of a chemoselective synthetic method to phosphorylate Cys side-chains in unprotected peptides. This approach makes use of a reaction between nucleophilic phosphites and electrophilic disulfides accessible by standard methods. We achieve the stereochemically defined phosphorylation of a Cys residue and verify the modification using electron-transfer higher-energy dissociation (EThcD) mass spectrometry. To demonstrate the use of the approach in resolving biological questions, we identify an endogenous Cys ph

SUBMITTER: Bertran-Vicente J 

PROVIDER: S-EPMC5025809 | biostudies-literature | 2016 Sep

REPOSITORIES: biostudies-literature