From transient sulfenic acids toward peculiar sulfurated molecules

GRAPHICAL ABSTRACT

ABSTRACT

Sulfenic acids (R-SOH) frequently act as reactive intermediates in biological and synthetic chemistry. Among the numerous examples that Nature offers to our knowledge, cysteine-derived sulfenic acids are recognized as key intermediates in signal transduction, transcriptional regulation events, and oxidative stress response. They also play catalytic and structural roles in enzymes. Furthermore, the sulfenic function is involved in the biosynthesis of thiosulfinates that give the characteristic odor and flavor to the Allium species and in the lachrymatory process of cut onion. On the other hand, the electronic nature of their S–O bond and its involvement in various, often stereospecific, reactions have prompted many applications of sulfenic acids in organic synthesis, such as their use as key intermediates in the preparation of peculiar sulfurated molecules. This paper aims at summarizing recent contributions on the generation and use of transient sulfenic acids in the stereocontrolled synthesis of sulfoxides and disulfides. These substrates offer a wide range of synthetic opportunities such as the synthesis of sulfinyl dienes to be involved in stereoselective DA reactions, the preparation of libraries of bioactive sulfurated molecules, the synthesis of unsymmetrical disulfides and tripodal sulfoxides and disulfides.

KEYWORDS:

• Sulfenic acids
• vinyl sulfoxides
• unsymmetrical disulfides
• thiacyclophanes
• thiaglycoconjugates