Pd-Catalyzed Coupling of Thioamides with N-Tosylhydrazones/Trapping by Esters Cascade Reaction

N,N-Disubstituted thioamides coupled with N-tosylhydrazones under Pd(TFA)₂/BuXPhos catalyst and NaOBu, and the intermediates from palladium carbene migratory insertion containing β-hydrogen were trapped by intramolecular esters activated by BF₃·Et₂O instead of undergoing β-H elimination, providing polyfunctional thiophen-3(2H)-ones with sulfur-containing tetrasubstituted carbon centers in moderate to good yields. The reaction features the formation of three bonds in a single operation, odorless, safe, and easily available substrates, wide substrate scope, and excellent functional group tolerance.