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On the Reactions of Thiols, Sulfenic Acids, and Sulfinic Acids with Hydrogen Peroxide
Author(s) -
Chauvin JeanPhilippe R.,
Pratt Derek A.
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201610402
Subject(s) - sulfenic acid , chemistry , sulfinic acid , hydrogen peroxide , thiol , substituent , redox , yield (engineering) , catalysis , organic chemistry , combinatorial chemistry , photochemistry , cysteine , enzyme , materials science , metallurgy
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.