Ru(II)‐Catalyzed Divergent Amidation and Homocoupling of β‐Ketosulfoxonium Ylides: Selective Access to α‐Ketoamides and α,α,β‐Tricarbonyl Sulfoxonium Ylides

A divergent Ru(II)‐catalyzed protocol for the efficient transformation of β‐ketosulfoxonium ylides into two distinct molecular scaffolds under mild conditions has been developed. In the presence of [Ru( p ‐cymene)Cl 2 ] 2 and Cu(OAc) 2 ·H 2 O, selective amidation with primary or secondary amines provides biologically relevant α‐ketoamides, whereas homocoupling in the absence of amines affords less explored α,α,β‐tricarbonyl sulfoxonium ylides. Both pathways proceed via a common Ru‐carbene intermediate and exhibit broad substrate scope and functional group tolerance. The synthetic utility is further demonstrated by downstream transformations, including heterocycle formation and late‐stage modifications.