A direct electrochemical oxidative cross dehydrogenative coupling reaction between enamines and thiophenols has been demonstrated. This strategy provides an effective, more economical, and environmentally friendly method to construct the C(sp2)‐S bond in the absence of chemical oxidants and transition metal catalysts. A variety of enamines and (hetero)aryl thiols are compatible with this transformation to afford the corresponding vinyl sulfides in moderate to excellent yields under undivided electrolytic cell conditions.

A mild and efficient functionalization of 8‐aminoquinolines has been demonstrated through the acylation and regioselective C5‐H halogenation in one pot under transition metal free conditions. This method enables the acyl halides acting as the donors of both acyl and halide atoms. Moremover, different type of acyl halides could be employed in this reaction and proceeded smoothly to afford the corresponding halogenated products in moderate to good yields. The protocol is operationally simple, facile, and might have potential application in synthesis of 5‐halogenated quinoline scaffolds.