Mechanistic aspects of the reaction of dimedone derivatives with sulfenic acids and other sulfur compounds—a computational study

Mechanism of the cysteine sulfenic acid O-sulfenylation of 1,3-cyclohexanedione

“…1) to form sulfides (thioethers). [1][2][3] In this manuscript, the investigation of an alternative reaction that leads to sulfenic ester formation through O-sulfenylation is presented and supported (Fig. 1).…”

DFT Study To Explore the Importance of Ring Size and Effect of Solvents on the Keto–Enol Tautomerization Process of α- and β-Cyclodiones

“…Research efforts have been put forward to design systems to improve the enol content. Keto–enol tautomerization has been observed in many biological processes that directly or indirectly proceed through keto–enol or amino–imino tautomerism, e.g., pyranose to furanose ring conversion of cyclic carbohydrate, glucose to fructose conversion, etc. − Keto–enol tautomerism also plays an important role in the formation of kynurenic acid, an antiexcitotoxic and anticonvulsant compound, which is generated due to the metabolism of l -tryptophan. − In the keto–enol tautomerization equilibrium process, one proton transfers from the α-carbon center to carbonyl oxygen through space via bond formation. − This proton transfer process is accelerated in the presence of solvent molecules or by suitable substituents. − In the case of acyclic ketone, reports reveal that the keto form is more stable in a polar solvent compared with the enol forms …”

Strecker degradation of amino acids promoted by a camphor-derived sulfonamide

“…Such a proton migration must of course be catalyzed, and water is an obvious candidate as catalyst. Indeed, water inclusion in reaction paths with high-lying transition states is often observed in water as solvent, as in biochemical reactions, and was demonstrated for, e.g., the analytical detection of sulfenic acids with dimedone [ 36 ]. In these systems water can act as proton shuttle.…”