To create your abstract, type over the instructions in the template box below. Fonts or abstract dimensions should not be changed or altered.

A catalytic amount of electrochemically generated "ArS+" ("ArS+" = ArS(ArSSAr)+) initiates a cation chain reaction of dienes that involves the addition of ArSSAr associated with stereoselective intramolecular carbon-carbon bond formation, and the direct (in-cell) electrolysis of a mixture of a diene and ArSSAr with a catalytic amount of electricity also effectively initiates the reaction.

The reaction of alkenes and alkynes with ArS(ArSSAr)+BF4−, which was generated and accumulated by the low-temperature anodic oxidation of ArSSAr in Bu4NBF4/CH2Cl2, led to the addition of an ArS group and fluoride across the carbon–carbon multiple bond to give thiofluorinated compounds in good yields.

The treatment of an olefinic thioacetal with a catalytic amount of ArS(ArSSAr)+B(C6F5)4−, or the electrolysis of a mixture of an olefinic thioacetal and ArSSAr, gives rise to effective intramolecular carbon–carbon bond formation (see scheme). This transformation opens up great potential for electroinitiated cation chain reactions in organic synthesis.

The addition reactions of diaryl disulfides (ArSSAr) to alkenes and alkynes were achieved with a catalytic amount of an arylbis(arylthio)sulfonium ion (ArS(ArSSAr)+), which was generated and accumulated by low‐temperature electrolysis of ArSSAr, to give the corresponding diarylthiolated products. The electrolysis of a mixture of ArSSAr and an alkene with a catalytic amount of electricity was also effective to drive the reactions. A cation chain mechanism mediated by ArS(ArSSAr)+ as a chain carrier is suggested.