p−π conjugation enriches electron density and facilitates the reactivity of adjacent π systems while simultaneously constraining electron mobility in subsequent transformations. Building on prior sulfur oxide chemistry, we leverage disruption of inherent p−π conjugation to enable halonium-mediated dearomative difunctionalization of benzothiophenes. As a result, mild dearomative difunctionalization converts planar benzothiophenes into structurally enriched three-dimensional counterparts, which can be further transformed into peripherally functionalized planar benzothiophene derivatives.
Shen et al. (Thu,) studied this question.