Brief introduction of Bis(tri-tert-butylphosphine)palladium

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(Chemical Equation Presented) Isolated truth: The synthesis, structures, and reductive elimination chemistry of arylpalladium(II) phenoxide and alkoxide complexes with a single bulky phosphine ligand are reported. These complexes are true intermediates in palladium-catalyzed etherification of aryl halides. They undergo reductive elimination of the alkyl aryl ether directly from the isolated complex (see scheme), and the rates of these reductive eliminations are slower than those from related arylpalladium amido complexes. Ad = adamantyl.

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

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Reference of 32005-36-0, Because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward and the reverse reactions by the same amount.32005-36-0, Name is Bis(dibenzylideneacetone)palladium, molecular formula is C34H28O2Pd. In a article,once mentioned of 32005-36-0

The ionic [Pd(C7H8C(O)R)(Ar-BIAN)]X (R = Me, Et, iPr, Ph; X = Cl, Br, I; Ar = p-An, P-FC6H4, P-BrC6H4, p-Tol, Ph, o,o?-Me2C6H3,o,o?-iPr 2C6H3) complexes (1b-12b), bearing the bidentate nitrogen ligand bis(arylimino)acenaphthene (Ar-BIAN), have been synthesized via reaction of the corresponding neutral acylpalladium complexes Pd(C(O)R)X(Ar-BIAN) (1a-12a) with norbornadiene (nbd). For the first time, an extensive kinetic study of this migratory alkene insertion into acyl-palladium bonds of neutral complexes containing alpha-diimine ligands has been carried out. It has been found that under pseudo-first-order circumstances these reactions follow the rate law kobsd = k1 + k2[nbd], which shows that these reactions proceed via a pathway independent of alkene concentration (k1 pathway) and a pathway dependent on alkene concentration (k2 pathway). The dramatic decrease of the rate constants k1 and k2 upon increasing the steric bulk of the BIAN ligand and the large negative entropy of activation and low enthalpy of activation for both pathways indicate that the k1 and k2 pathways are closely related and involve associative processes. From the influence of solvent, X and C(O)R ligand, steric and electronic properties of the BIAN ligand, the presence of free halide and free BIAN, and the parameters of activation, mechanisms have been proposed for both pathways. The k1 pathway may proceed via a rate-determining solvent-assisted halide or nitrogen dissociation, followed by alkene association and migratory insertion, while the k2 pathway may occur via a rate-determining migratory alkene insertion in a contact ion pair intermediate. This species may be formed via alkene association followed by either halide or nitrogen dissociation.

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

Archives for Chemistry Experiments of Bis(dibenzylideneacetone)palladium

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The Pd-catalyzed 3-arylation of 2-oxindoles with aryl bromides, chlorides and triflates is found to proceed using i -Pr-BI-DIME and Me 2 -BI-DIME ligands. The mono-arylation of 3-unsubstituted oxindoles is accomplished using a Pd 2 (dba) 3 / i -Pr-BI-DIME catalyst system, and gives good yields of 3-aryloxindoles from aryl bromides and chlorides. The arylation of 3-substituted oxindoles is also possible using this catalyst/ligand system. The asymmetric arylation of 3-substituted oxindoles is accomplished using Me 2 -BI-DIME to furnish oxindoles bearing a quaternary C-3 stereocenter in enantiomeric ratios of up to 93:7.

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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 present invention relates to compounds of Formula (I), and solvates, hydrates, and pharmaceutically acceptable salts thereof, wherein X1, X1′, X1″, R1, R2 and R3 are as defined herein, useful as FLAP modulators. The invention also relates to pharmaceutical compositions comprising compounds of Formula (I). Methods of making and using the compounds of Formula (I) are also within the scope of the invention.

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

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Construction of sterically congested all-carbon quaternary centers represents a formidable challenge in synthetic chemistry. The method described herein provides direct and facile access to a series of structurally diverse and synthetically useful aliphatic aldehydes, bearing an all-carbon alpha-vinyl quaternary center and a 1,5-diene functionality, through Pd-catalyzed umpolung of vinylethylene carbonates (VECs). The reaction features electrophilic-to-nucleophilic reactivity reversal of the VEC-derived pi-allyl-palladium intermediate via an unusual beta-hydride elimination process, and the resultant enolate is chemoselectively coupled with allylic acetate to form an alpha-vinyl aldehyde embedded with an all-carbon quaternary center.

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

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A new method for the synthesis of highly substituted allyl azides by carboazidation of allenes catalyzed by palladium complexes is described. Treatment of 1,1-dimethylallene (1a) with an aromatic iodide ArI 2 (4-CH3COC6H4I, 4-CH3OC6H4I, 3-CH3OC6H4I,4-CH3C6H 4I, 3-CH3C6H4I, 3-C2H5OCOC6H4I,4-C2H 5OCOC6H4I, 4-ClC6H4I, 3-BrC6H4I or 1-iodothiophene), (CH3)3SiN3 and KOAc in the presence of Pd(dba)2 (dba = dibenzylideneacetone) in DMF at 70 C gave two regioisomers (CH3)2CC(Ar)CH2N3 3 and (CH3)2(N3)CC(Ar)CH2 4 in good to excellent yields. The observed regio- and stereoisomer ratios of the allyl azides from these reactions are close to the equilibrium ratio of these isomers at ambient temperature due to a rapid 1,3-shift of the azido group. Reduction of a mixture of 3a and 4a (80:20, Ar = 4-C6H4COMe) by PPh3-H2O afforded only the sterically less hindered (CH3)2C=C(Ar)-CH2NH2 in 95% yield further supporting a rapid 1,3-azide shift of 3a and 4a. Mono-substituted allenes RCHCCH2 also undergo carboazidation with aryl iodides and (CH3)3SiN3 in good to excellent yields. For n-butyl-, cyclopentyl-and cyclohexylallene (1b-d), carboazidation gives three isomers 5, 6 and 7 in ca. 1:1:1 ratio. For phenyl- and phenoxyallene (1e and f), the reaction produces two stereoisomers Z- (5) and E-CHR=C(Ar)CH2N3 (6), where R = Ph and PhO; the regioisomer RCH(N3)C(Ar)=CH2 (7) was not observed. In contrast, carboazidation of tert-butylallene (1g) afforded regioisomer t-BuHC(N3)C(Ar)=CH2 as the major product (?90% yield). Based on known palladium-allene and -allyl chemistry, a mechanism is proposed to account for this palladium-catalyzed three-component assembling reaction. The Royal Society of Chemistry 2000.

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

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A series of disilane-bridged donor-acceptor architectures 1-9 containing strong electron-donating and -withdrawing substituents were designed and synthesized in acceptable yields. The substituents substantially affected the fluorescence and nonlinear optical properties of the compounds. In the solid state, the compounds showed purple-blue fluorescence (lambdaem = 360-420 nm) with high quantum yields (up to 0.81). Compound 3, which had p-N,N-dimethylamino and o-cyano substituents, exhibited optical second harmonic generation (activity 2.9 times that of urea, calculated molecular hyperpolarizability beta = 1.6 × 10-30 esu) in the powder state. Density functional theory calculations for the ground and excited states indicated that both the locally excited state and the intramolecular charge transfer excited state make important contributions to the luminescence behavior.

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

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A strategy for the synthesis of the lycopodium alkaloid dihydrolycolucine (1) has been investigated. Synthetic routes were developed based on N-acylpyridinium salt chemistry to prepare target fragments 3 and 4 that could ultimately converge to the natural product. Key reactions include IMDA cycloadditions and retro-Mannich ring-openings to form both the AB and the EF ring fragments. The ring C precursor was prepared using pyridine substitution and directed lithiation chemistry. A Suzuki cross-coupling of rings C and EF led to the CEF ring fragment. Initial attempts at closure of the seven-membered D ring were unsuccessful.

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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 activation of the inert C-O bonds in mesylates through the use of a new class of imidazolyl phosphines allows the decarboxylative coupling of aryl mesylates as well as polysubstituted alkenyl mesylates. Variation of the ligands leads to two complementary methods providing the corresponding biaryls and polysubstituted olefins in good yields. Copyright

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

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Four three-coordinate arylpalladium amido complexes with a single hindered phosphine were isolated and structurally characterized. Each possessed a T-shaped geometry. Several of these complexes possessed true three-coordinate structures that lacked any additional coordination by ligand C-H bonds. All of the three-coordinate complexes underwent reductive elimination to form the corresponding triarylamine. A comparison of the rate of reaction of the three-coordinate compounds demonstrated that the rate of elimination from the pentaphenylferrocenyl di-tert-butylphosphine complex were the fastest. A comparison of the rates of reactions between three-coordinate and four-coordinate complexes showed that the rates were much faster from the three-coordinate complexes. Copyright

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