Palladium, Bis[tris(1,1-dimethylethyl)phosphine]

Shaughnessy, Kevin H.

doi:10.1002/047084289x.rn00776

Cited by 2 publications

(1 citation statement)

References 34 publications

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“…Homoleptic complexes, such as Pd (PPh 3 ) 4 , have long been used as catalyst precursors. Those based on more sterically demanding, electron-rich ligands, such as Pd(P(o-tol) 3 ) 2 , [16] Pd(P(t-Bu) 3 ) 2 [17] or Pd(IPr) 2 , [18] have also been applied catalytically. Ligand dissociation from the L 2 Pd(0) complexes often occurs with a relatively high barrier, which makes these precatalysts slow to initiate at lower temperatures.…”

Section: Pd(0) Precatalystsmentioning

confidence: 99%

Development of Palladium Precatalysts that Efficiently Generate LPd(0) Active Species

Shaughnessy

2019

Israel Journal of Chemistry

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Palladium catalysts have become central to modern organic synthesis, particularly in the context of crosscoupling reactions to form CÀ C and C-heteroatom bonds. The development of highly efficient catalyst systems has seen a transition from the use of in situ-generated catalysts derived from a ligand source and palladium precursor to the use of preformed palladium-ligand complexes that can efficiently generate the active species. The design of these systems has focused on optimizing the generation of the LPd(0) species presumed to be the active catalysts with most state-of-the-art ligand systems. This review will highlight the development of Pd(0), Pd(I), and Pd(II) precatalysts that efficiently generate LPd(0) active species with a focus on their activation mechanisms and applications in catalysis. Scheme 3. Synthesis of diene-stabilized LPd(0).Scheme 4. COD-stabilized LPd(0) and application to fluorination reactions. Scheme 14. Activation routes for Pd(allyl) precatalysts. Scheme 15. Competition between formation of active species and inactive μ-allyl palladium(I) dimers.

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Section: Pd(0) Precatalystsmentioning

confidence: 99%

Development of Palladium Precatalysts that Efficiently Generate LPd(0) Active Species

Shaughnessy

2019

Israel Journal of Chemistry

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Air-Stable [(R₃P)PdCl₂]₂Complexes of Neopentylphosphines as Cross-Coupling Precatalysts: Catalytic Application and Mechanism of Catalyst Activation and Deactivation

et al. 2018

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Air-stable [(R3P)PdCl2]2 complexes with di-tert-butylneopentylphosphine (DTBNpP, 1a) or trineopentylphosphine (TNpP, 1b) ligands have been applied to Suzuki cross-coupling reactions, and the mechanism of their conversion to the active LPd0 catalyst species has been studied. Precatalysts 1a,b provide effective catalysts for Suzuki cross-coupling of aryl bromides at room temperature, even when the reactions are performed in air. The precatalyst systems provided much higher activity catalysts in toluene/water in comparison to acetonitrile/water. Precatalyst loadings could be decreased by a factor of 50 in toluene in comparison to acetonitrile, while achieving equal or better yields. In acetonitrile/water, ligand metalation to form a [(κ2-P,C-DTBNpP)PdX]2 palladacycle was found to compete with formation of the active Pd(0) species. The palladacycle shows low catalytic activity; thus, its formation represents a catalyst deactivation pathway. In toluene, clean formation of the active Pd(0) species occurs without competitive palladacycle formation. The improved selectivity to form the active Pd(0) species in toluene appears to account for the higher activity of the precatalysts in toluene/water.

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Palladium, Bis[tris(1,1-dimethylethyl)phosphine]

Cited by 2 publications

References 34 publications

Development of Palladium Precatalysts that Efficiently Generate LPd(0) Active Species

Development of Palladium Precatalysts that Efficiently Generate LPd(0) Active Species

Air-Stable [(R₃P)PdCl₂]₂Complexes of Neopentylphosphines as Cross-Coupling Precatalysts: Catalytic Application and Mechanism of Catalyst Activation and Deactivation

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Palladium, Bis[tris(1,1-dimethylethyl)phosphine]

Cited by 2 publications

References 34 publications

Development of Palladium Precatalysts that Efficiently Generate LPd(0) Active Species

Development of Palladium Precatalysts that Efficiently Generate LPd(0) Active Species

Air-Stable [(R3P)PdCl2]2Complexes of Neopentylphosphines as Cross-Coupling Precatalysts: Catalytic Application and Mechanism of Catalyst Activation and Deactivation

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Air-Stable [(R₃P)PdCl₂]₂Complexes of Neopentylphosphines as Cross-Coupling Precatalysts: Catalytic Application and Mechanism of Catalyst Activation and Deactivation