Theoretical Analysis of Factors Controlling Pd-Catalyzed Decarboxylative Coupling of Carboxylic Acids with Olefins

摘要: Transition-metal-catalyzed decarboxylative coupling presents a new and important direction in synthetic chemistry. Mechanistic studies on not only improve the understanding of newly discovered transformations, but also may have valuable implications for development more effective catalyst systems. In this work, comprehensive theoretical study was conducted mechanism Myers’ Pd-catalyzed Heck reaction. The catalytic cycle found to comprise four steps: decarboxylation, olefin insertion, β-hydride elimination, regeneration. Decarboxylation rate-limiting step, it proceeded through dissociative pathway which Pd(II) mediated extrusion CO2 from an aromatic carboxylic acid form Pd(II)−aryl intermediate. Further analysis factors that might control efficiency These included Pd salts, ligands, substrates, metals. (1) Regarding ...