Aminophosphine Palladium Pincer-Catalyzed Carbonylative Sonogashira and Suzuki–Miyaura Cross-Coupling with High Catalytic Turnovers

Abstract

This work documents the first palladium pincer complex-catalyzed carbonylative Sonogashira (CS) and carbonylative Suzuki-Miyaura (CSM) cross-coupling. Compared to previous protocols, which employ hazardous and toxic solvents, the aminophosphine pincer complex {[C₆H₃-2,6-(NHP{piperidinyl}₂)₂]Pd(Cl)} (<b>III</b>) catalyzes both the cross-coupling reactions in propylene carbonate, an eco-friendly and sustainable polar aprotic solvent. Advantageously, employing <b>III</b> allows the CS cross-coupling to be carried out at a palladium loading of 10^-4 mol % and the CSM cross-coupling to be carried out at 10^-6 mol %, thus resulting in catalytic turnovers of 10⁵ and 10⁷, respectively. Relative comparison of the pincer complex with conventional palladium precursors Pd(OAc)₂ and PdCl₂(PPh₃)₂ shows the efficiency and robustness of the pincer complex in effecting higher catalytic activity at low palladium loadings.