Thioenols from Peptidyl Cysteines: Oxidative Decarboxylation of a ¹³C‐Labeled Substrate

Abstract

A key player in the biosynthesis of epidermin, the novel enzyme EpiD converts peptidyl cysteines into thioenols [Eq. (a)]. The thioenols are unstable and decompose within hours. The oxidative decarboxylation of a 13C-labeled peptide substrate was monitored by mass spectrometry and NMR spectroscopy, and the structure of the intermediate in the biosynthesis was determined. R = peptide residue.