Addition of sulfenic acids to monosubstituted acetylenes : a theoretical and experimental study

The reaction of benzenesulfenic acid, generated in situ by thermal decomposition of 3-(phenylsulfinyl)propanenitrile, with monosubstituted acetylenes was experimentally and theoretically investigated at the DFT level using the MPW1B95 density functional. A computational model based on the Hard Soft Acid Base (HSAB) principle was evaluated for its ability to qualitatively and quantitatively predict the regioselectivity, while kinetics and thermodynamics of the reaction were studied through the analysis of the reaction paths leading to the possible regioisomers