Electrochemical Selective C(sp3)–S/C(sp2)–S Bond Cleavage of Heteroaryl Alkyl Sulfides

Comprehensive Summary An electrochemically mediated selective C(sp 3 )–S/C(sp 2 )–S bond cleavage of heteroaryl alkyl sulfides has been developed. This conversion features transition‐metal‐, oxidant‐ and catalyst‐free conditions, involving dealkylation or desulfuration transformation with operational simplicity and good functional group tolerance. Besides, scale‐up experiments and single‐path continuous‐flow electrosynthesis were used to demonstrate the potential of this transformation in practical organic synthesis.