B(C 6 F 5 ) 3 -Catalyzed Regiodivergent Thioetherifications of Alkenes via Thiiranium Intermediates: Experimental and Computational Insights

Precise control of selective alkene functionalization is a continuing challenge in the chemical community. In this study, we develop a substitution-controlled regiodivergent thioetherification of di- or trisubstituted alkenes using 10 mol % tris(pentafluorophenyl)borane [B(C F ) ] as a catalyst and N-thiosuccinimide as a sulfenylating reagent. This metal-free borane catalyzed C-S bond forming method is utilized for a Csp -H sulfenylation reaction to synthesize an array of diphenylvinylsulfide derivatives with good to excellent yields (25 examples, up to 91 % yield). Some of the products exhibit aggregation-induced emission luminogen properties used in organic light-emitting diodes (OLEDs), chemical sensors, and biological imaging units. Depending upon the starting alkene, Csp -S sulfenylation products could also be generated regioselectively. A variety of allylic thioethers from α-alkyl substituted styrenes were isolable in good yields and selectivities (14 examples, up to 67 % yield). The DFT-supported mechanistic study confirms that the reaction proceeds via a thiiranium ion intermediate, where the regioselectivity and product formation is determined by the alkene substituents which influence the activation barriers and energy profiles. Diphenylvinylsulfide derivatives can also be efficiently transformed into a range of synthetically valuable compounds, including vinyl sulfoxides, vinyl sulfones, and vinyl sulfoximines.