Palladium-Catalyzed Tandem Ester Dance/Decarbonylative Cou-pling Reactions

“Dance reaction” on the aromatic ring is a powerful method in organic chemistry to translocate functional groups on arene scaffolds. Notably, dance reactions of halides and pseudo-halides offer a unique platform for the divergent synthesis of substituted (het-ero)aromatic compounds when combined with transition-metal-catalyzed coupling reactions. Herein, we report a tandem reaction of ester dance and decarbonylative coupling enabled by palladium catalysis. In this reaction, 1,2-translocation of the ester moiety on the aromatic ring is followed by decarbonylative coupling with nucleophiles to enable the installation of a variety of nucleophiles at the posi-tion adjacent to the ester in the starting material. The key to this reaction is to use dcypt, an electron-rich, bulky diphosphine ligand. Vari-ous decarbonylative couplings such as C–H arylation, amination, intramolecular etherification, and intermolecular arylation are success-fully executed following the ester dance.