This study demonstrated for the first time that alkenoic thioesters can be effectively used as nucleophiles in ring-closing disulfenylation reactions. Our investigation revealed that the reaction in hexafluoroisopropanol with an electrophilic sulfur reagent significantly enhances the product yield. We gathered experimental and theoretical evidence to support the superiority of thioesters over the traditionally used benzyl sulfide. Additionally, we explored the substrate scope and identified various factors affecting the reaction selectivity and yield.