Exploiting Aryl Mesylates and Tosylates in Catalytic Mono-α-arylation of Aryl- and Heteroarylketones

The first general palladium catalyst for the catalytic mono-α-arylation of aryl- and heteroarylketones with aryl mesylates and tosylates is described. The newly developed indolyl-derived phosphine ligand L7 has been identified to promote this reaction efficiently. The key to success is attributed to the enhanced steric congestion of the catalyst and effective oxidative addition of the C_(Ar)-OMs bond. In the presence of Pd(OAc)₂ (0.25-2.5 mol %) and L7, selective monoarylations are achieved with ample reaction scope and product yields up to 95%. Importantly, we demonstrated the applicability of this protocol with the modification of biological phenolic compounds, rendering it amenable for functionalization of phenolic (pro)drugs. © 2016 American Chemical Society.