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

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.

Post-Modification of Octahedral Chiral-at-Metal Cobalt(III) Complexes by Suzuki–Miyaura Cross-Coupling and Evaluation of Their Catalytic Activity

“…Suzuki–Miyaura cross-coupling reaction (CCR) is the most powerful tool for the formation of new C–C bonds in order to construct complex molecules in one step . Albeit the Suzuki–Miyaura CCR was broadly applied for the modification and functionalization of chiral organic ligands, the usage of these type reactions for the direct modification of metal complexes is still limited .…”

Trichloromethyl Carbanion in Aqueous Micelles: Mechanistic Insights and Access to Carboxylic Acids from (Hetero)aryl Halides

“…Likewise, Pd ligated with cBRIDP provided a slightly better yield (29%, entry 6). Notably, the ferrocene-based electron-rich bulky ligand, QPhos, afforded 2 in 61% isolated yield and indicated that electron-rich monodentate phosphine ligands are critical for the optimal activity (entry 7). , t -BuXPhos, another bulky ligand, was ineffective for this transformation (entry 8).…”

“…Aryl bromides bearing active methyl (13,25) or methylene (14, 19) groups afford the corresponding acids without unwanted α-arylated byproducts. Substrates containing other important functional groups, such as nitriles (19,34), ethers (8,24,26,33,35,37), trifluoromethyl (6,7,24), tert-amine (10), and carbamate (15) exhibited good reactivity. Although the reaction based on the conversion as determined by in-process NMR analysis was good-to-excellent, the isolated yield of the substrate containing dibenzyl amine (10) was poor.…”

Introducing Savie: A Biodegradable Surfactant Enabling Chemo- and Biocatalysis and Related Reactions in Recyclable Water

“…This allows otherwise water-sensitive and insoluble compounds to be dispersed within a bulk aqueous medium. Another virtue associated with micellar catalysis is that the close proximity of reagents and catalysts within the micellar core leads to characteristically high concentrations, and thereby faster reaction rates …”