Palladium-Catalyzed/Copper-Mediated Decarbonylative Cross-Coupling of S-Pyrimidyl Thioesters for Biaryl Synthesis

A palladium-catalyzed/copper-mediated cross-coupling of S-pyrimidinyl thioesters with arylboronic acids to yield biaryls is described. The reaction is likely to proceed via cleavage of the S–C(O) bond and subsequent release of CO, rather than via cleavage of the S–C(pyrimidine) bond and release of SCO, as supported by the results of both experimental and computational studies. The investigation of the reaction scope with various S-pyrimidinyl thioesters and arylboronic acids showed that the reaction is significantly affected by the substituent of the thioester and the presence of a chelatable ortho substituent was found to increase reaction efficiency.