Deacylative Thiolation by Redox‐Neutral Aromatization‐Driven C−C Fragmentation of Ketones

Abstract Herein we report the development of deacylative thiolation of diverse methyl ketones. The reaction is redox‐neutral, and heavy‐metal‐free, which provides a new way to introduce thioether groups site‐specifically to unactivated aliphatic positions. It also features excellent functional group tolerance and broad substrate scope, thus allowing late‐stage derivatization. The process benefits from efficient condensation between the activation reagent and ketone substrates, which triggers aromatization‐driven C−C fragmentation and rapid radical coupling with thiosulfonates. Experimental and computational mechanistic studies suggest the involvement of a radical chain pathway.