On the Reactions of Thiols, Sulfenic Acids, and Sulfinic Acids with Hydrogen Peroxide

Abstract The reaction of thiols with H 2 O 2 is central to many processes essential to life, from protein folding to redox signaling. The initial products are assumed to be sulfenic acids, but their observation, and the kinetic and mechanistic characterization of their subsequent reactions, has proven challenging. The introduction of a 9‐fluorotriptycene substituent enabled the use of 19 F NMR to directly monitor the reaction of a thiol with H 2 O 2 to yield a sulfenic acid, and its subsequent oxidation to sulfinic and sulfonic acids. The oxidations are specific base catalyzed, as revealed by the lack of isotope effects and the dependence of the kinetics on pH but not buffer concentration.