Ligand-Controlled Acyl and Decarbonylative Sonogashira Cross-Coupling of α,β-Unsaturated Thioesters

A palladium-catalyzed ligand-controlled acyl and decarbonylative Sonogashira reaction of alkenyl thioesters with terminal alkynes was developed. 1,3-Enynes and enynone products were obtained by using 1,3-bis(diphenylphosphino)propane and P(3,5-(CF3)2C6H3)3 as the ligands, respectively. To demonstrate the synthetic utilities, late-stage constructions of 1,3-enyne and enynone skeletons in natural products and drugs were showcased.