Abstract: Methane-and benzenesulfenyl chloride afforded predominantly anti-Markovnikov oriented adducts with terminal alkyl substituted olefins and vinyl chloride. This adduct selectivity increased with increasing bulki-ness of the alkyl substituent of the substrate. These kinetically controlled adducts were found to readily undergo acid-catalyzed isomerization to the thermodynamically more stable Markovnikov adducts. Phenyl ...