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Emerging Trends in Cross-Coupling: Twelve-Electron-Based L₁Pd(0) Catalysts, Their Mechanism of Action, and Selected

Sharbil J Firsan¹, Vilvanathan Sivakumar², Thomas J Colacot¹

¹Science and Lab Solutions-Chemistry, MilliporeSigma, 6000 North Teutonia Avenue, Milwaukee, Wisconsin53209, United States.

Chemical Reviews

|October 3, 2022

Abstract:

Monoligated palladium(0) species, L₁Pd(0), have emerged as the most active catalytic species in the cross-coupling cycle. Today, there are methods available to generate the highly active but unstable L₁Pd(0) catalysts from stable precatalysts. While the size of the ligand plays an important role in the formation of L₁Pd(0) during in situ catalysis, the latter can be precisely generated from the precatalyst by various technologies. Computational, kinetic, and experimental studies indicate that all three steps in the catalytic cycle─oxidative addition, transmetalation, and reductive elimination─contain monoligated Pd. The synthesis of precatalysts, their mode of activation, application studies in model systems, as well as in industry are discussed. Ligand parametrization and AI based data science can potentially help predict the facile formation of L₁Pd(0) species.

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