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A series of arylpalladium alkyl complexes of the formula [(DPPBz)Pd(Ar)(R)] (DPPBz = 1,2-bis(diphenylphosphino)benzene; R = methyl, benzyl, enolate, cyanoalkyl, trifluoroalkyl, or malonate) has been prepared to reveal the influence of steric and electronic parameters on structure, stability, and reactivity. Arylpalladium enolate and cyanoalkyl complexes ligated by EtPh 22P, 1,1-bis(diisopropylphosphino)ferrocene (D iPrPF), and BINAP were prepared to evaluate the effect of the ancillary ligand. The coordination modes of the enolate and cyanoalkyl complexes were determined by spectroscopic methods, in combination with X-ray crystallography. In the absence of steric effects, the C-bound isomer was favored electronically if the enolate or cyanoalkyl group was located trans to a phosphine, and the O-bound isomer was favored if the enolate was located trans to an aryl group. The thermodynamic stability of the enolate and cyanoalkyl complexes was controlled by the steric properties of the enolate or cyanoalkyl group, and complexes with more substitution at the alpha-carbon were less stable. Arylpalladium methyl, benzyl, enolate, cyanoalkyl, and trifluoroethyl complexes underwent carbon-carbon bond-forming reductive elimination upon heating. Reductive elimination was faster from complexes with electron-withdrawing substituents on the palladium-bound aryl group and with sterically hindered alkyl groups. The electronic properties of the alkyl group had the largest impact on the rate of reductive elimination: electron-withdrawing groups on the alpha-carbon retarded the rate of reductive elimination. The rates of reductive elimination correlated with the Taft polar substituent constants of the groups on the carbon alpha to the metal.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

8-Sep-2021 News Properties and Exciting Facts About 69861-71-8

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Reference of 69861-71-8, Catalysts function by providing an alternate reaction mechanism that has a lower activation energy than would be found in the absence of the catalyst. In some cases, the catalyzed mechanism may include additional steps.In a article, 69861-71-8, molcular formula is C42H42P2Pd, introducing its new discovery.

Highly active but sterically demanding: Ambient-temperature Suzuki cross-coupling of aryl chlorides is possible with a palladium(o) complex bearing two bulky, N-heterocyclic carbene ligands (see structure). Nearly quantitative yields are obtained within two hours with some reagents, which makes this compound the most active catalyst known to date under these conditions.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Discovery of Bis(tri-o-tolylphosphine)palladium(0)

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Provided are methods for site- and stereo-retentive cross-couplings with unactivated secondary boronic acids, particularly useful in building block-based approach for small molecule synthesis. Also provided is a method of forming an air-stable chiral secondary boronic acid.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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This Communication describes studies of Ph-RF (RF = CF3 or CF2CF3) coupling at Pd complexes of general structure (PtBu3)PdII(Ph)(RF). The CF3 analogue participates in fast Ph-CF3 coupling (<5 min at 80 C). However, the formation of side products limits the yield of this transformation as well as its translation to catalysis. DFT and experimental studies suggest that the side products derive from facile alpha-fluoride elimination at the 3-coordinate PdII complex. Furthermore, they show that this undesired pathway can be circumvented by changing from a CF3 to a CF2CF3 ligand. Ultimately, the insights gained from stoichiometric studies enabled the identification of Pd(PtBu3)2 as a catalyst for the Pd-catalyzed cross-coupling of aryl bromides with TMSCF2CF3 to afford pentafluoroethylated arenes. If you are interested in 69861-71-8, you can contact me at any time and look forward to more communication. Application In Synthesis of Bis(tri-o-tolylphosphine)palladium(0)

Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Ligand exchange reactions reveal unexpected lability of the carbene ligands in two coordinate palladium(0) N-heterocyclic carbene complexes; the latter are found to be very effective catalysts for amination of aryl chlorides.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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Significant catalyst loading reduction and increased reaction robustness have been achieved for a Pd-catalyzed asymmetric intramolecular C-N coupling through comprehensive mechanistic studies. Detailed kinetic, spectroscopic, and crystallographic analyses revealed that the mono-oxidation of the bis-phosphine ligand is critical for a successful transformation. 31P NMR studies provided an understanding of the inefficient activation of the Pd(OAc)2/(R,R)-QuinoxP* pre-catalyst to form the active bis-phosphine mono-oxide-Pd(0) catalyst with competitive formation of a less active (R,R)-QuinoxP*·PdBr2 complex. Based on these detailed mechanistic studies, a new series of bis-phosphine mono-oxides (BPMO)-ligated Pd(ii) pre-catalysts have been rationally developed that allow for reliable and complete catalyst activation which should have general utility in academic and industrial settings.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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The invention concerns the preparation of a metal chelate, in particular a precious metal beta-diketonate or a precious metal phosphine complex MLaXb, where M is a metal atom, L is a ligand, X is an anion which is preferably a halide, HCO3¯, NO3¯, CO32E or carboxylate, a is a number equal to or less than the coordination number of the metal, b is 0, 1, 2 or 3, comprising reacting an ammine compound of metal M with a complexing compound, which is preferably a phosphine or a diketonate. Metal compounds which can be made by this process are also described.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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We describe herein formal syntheses of the indole alkaloids cis-trikentrin A and herbindole B from a common meso-hydroquinone intermediate prepared by a ruthenium-catalyzed [2+2+1+1] cycloaddition that has not been used previously in natural product synthesis. Key steps include a sterically demanding Buchwald?Hartwig amination as well as a unique C(sp3)?H amination/indole formation. Studies toward a selective desymmetrization of the meso-hydroquinone are also reported.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

Brief introduction of 69861-71-8

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Taking into consideration the model geometry of the macrocyclic hexaporphyrin 1 as a host molecule, the structure of a benzene-centered porphyrin trimer bearing pyridine rings at the apical positions has been designed with the aim to use the latter as a template for the synthesis of its own host. Indeed, in the presence of the porphyrin trimer 5, the yield of the cyclization of a linear porphyrin hexamer, as a precursor of 1, could be improved from 8 to 30% (variable yield) to 50% (reproducible yield). Even the condensation of equimolecular amounts of porphyrin monomers 20b and 21b in the presence of 5 led-probably through a loose preorganized complex between the latter and the Zn(II) chelate 20b-to the formation of 1 in only five steps from 19, as compared with 13 steps of the synthesis via linear porphyrin hexamer in the absence of template. As evidenced by 1H NMR spectroscopic analysis of the supramolecular complex between 5 and an analogue of 1b in which all H-atoms at the pyrrole rings have been replaced by deuterium, in the presence of unlabeled 1b, a rapid dissociation and recombination of the host and guest molecules forming the supramolecular complex takes place even at low temperature (-40 C). As at 55 C all six Zn(II) porphyrinate rings of the complex 1b + 5 become magnetically equivalent in the 500 MHz 1H NMR time scale, approximate kinetic data for the ligand exchange process could be obtained.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method

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In homogeneous catalysis, the catalyst is in the same phase as the reactant. The number of collisions between reactants and catalyst is at a maximum.In a patent, 69861-71-8, name is Bis(tri-o-tolylphosphine)palladium(0), introducing its new discovery. name: Bis(tri-o-tolylphosphine)palladium(0)

The Pd-catalyzed alkoxycarbonylation of 4-bromoacetophenone with n-butanol to provide the corresponding benzoic acid ester was studied systematically by evaluating the effect of critical reaction parameters, i.e., temperature, CO pressure, solvent, base, catalyst precursor, and ligand/Pd ratio. At 100-130C, the catalyst exhibited the highest efficiency using 4-bromoacetophenone/n-butanol system. CO pressure showed substantial influence on the catalyst productivity. Neat alcohol was the best solvent for the reaction. The catalysts precursors Pd(PPh3)4 or a combination of PdCl2(PhCN)2/80 equivalence gave the best productivities. Sodium acetate and sodium carbonate led to significantly lower ester yields than the amine bases. The P/Pd ratio variation in PPh3 showed an optimum value of ~ 8 equivalence of the ligand to Pd under the reaction conditions (0.1 mole % PdCl2(PhCN)2, 1.2 equivalence NEt3, 14 ml n-butanol, 5 bar CO, and 130C) for high catalyst stability and activity.

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Reference:
Chapter 1 An introduction to palladium catalysis,
Palladium/carbon catalyst regeneration and mechanical application method