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An enantiospecific palladium-catalyzed decarboxylative coupling of acyclic beta,gamma-alkynoic acids with various aryl iodides to chiral tetrasubstituted allenes is described. The coupling reaction comprises a decarboxylative gamma-palladation of alpha,alpha-disubstituted carboxylic acids to provide the tetrasubstituted allenes with complete point-to-axial chirality transfer in excellent yields.

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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 Pd atom in the title compound, [Pd(C6H5S)2-(C22H 36FeP2)], possesses a distorted square-planar geometry. The phenyl rings attached to the S atoms are located on opposite sides of the plane defined by the Pd and two S atoms. The Pd – S bonds are statistically significantly different, with values of 2.3703 (7) and 2.3887 (7) A.

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

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Pesticidal 1,4-diaryl-2-fluoro-2-butene compounds having the structural formula I STR1 and compositions and methods comprising those compounds for the control of insect and acarid pests.

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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 coordination chemistry of the new bidentate nitrogen ligands 8-(2-pyridyl)quinoline (8-PQ) and 8-(6-methyl-2-pyridyl)quinoline) (Me-8-PQ) towards palladium and platinum has been studied. Several (N?N)Pd(R)Cl and (N?N)Pd(alkene) complexes have been synthesised. The complex (8-PQ)Pd(Me)Cl has been characterised by a single crystal X-ray determination (crystal data: triclinic space group P 1 with a=8.513(5), b=9.338(4), c=10.219(2) A, alpha=108.11(2), beta=89.82(3), gamma=116.81(4), V=680.1(6) A3, R=0.033, Z=2). A fast CO insertion occurs into the palladium-carbon bond of the complexes (N?N)Pd(Me)Cl providing the (N?N)Pd(C(O)Me)Cl complexes. For (8-PQ)Pd(C(O)Me)Cl an X-ray structure determination has been carried out (crystal data: monoclinic space group P21/c with a=9.084(4), b=10.179(3), c=16.400(3) A, beta=95.59(2), V=1509.2(9) A3, R=0.043, Z=4). Unexpected in both molecular structures is the large dihedral angle between the plane of the bidentate nitrogen ligand and the coordination plane of the palladium. Both bidentate coordinating ligands 8-PQ and Me-8-PQ show a relatively large bite angle. A monodentate coordination mode has been observed for the complexes (N?N)M(PEt3)Cl2 (M=Pd, Pt), as the pyridyl group of the ligand is coordinated to the metal while the quinoline group is dissociated from the metal, which is shown in the X-ray structure determination for the complex (8-PQ)Pd(PEt3)Cl2 (crystal data: monoclinic space group P21/a with a=15.736(2), b=7.782(1), c=18.255(3) A, beta=102.98(1), V=2178.3(6) A3, R=0.062, Z=4).

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

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5-Carbapterocarpens, one of them displaying estrogenic activity, were prepared from alpha-aryltetralones in high yields through a one-pot, BBr3-promoted O-demethylation and cyclization sequence. The key alpha-aryltetralone intermediates were obtained by direct alpha-arylation of tetralones with o-alkoxybromoarenes in the presence of Pd2(dba)3 (2.5 mol-%) and tBu3PHBF4 (10 mol-%) as catalysts, together with 2.5 equiv. of KOH in dioxane/H2O (4:1), under microwave irradiation conditions (80 W, 100 C, 40 min), leading to alpha-monoaryltetralones in good yields.

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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, 53199-31-8, name is Bis(tri-tert-butylphosphine)palladium, introducing its new discovery. Recommanded Product: 53199-31-8

The compounds Pd(eta3-1-Ph-C3H4) (eta5-C5H5) (I), Pd2(dba) 3 (II), Pd(OAc)2 (III), and [Pd(eta3-1-Ph- C3H4)Cl]2 (IV) are frequently utilized as catalyst precursors for a variety of cross-coupling processes, including Suzuki-Miyaura, Heck-Mizoroki, Sonogashira, and Buchwald-Hartwig reactions. In the preceding paper in this issue, we assess and compare catalyst systems based on I-IV activated with PBut3, XPhos, and/or Mor-Dalphos for the prototypical Buchwald-Hartwig amination reactions of 4-bromo- and 4-chloroanisole with morpholine, noting several apparent incongruities which seem to indicate mechanistic dissimilarities for various reactant/precatalyst combinations. In this paper we investigate by NMR spectroscopy the solution chemistry of I and IV with PBut3, XPhos, and Mor-Dalphos, noting similarities and differences in the respective abilities of these precursor-ligand combinations to generate palladium(0) catalyst systems. We find inter alia that steric requirements prevent Xphos and Mor-Dalphos from forming 2:1 palladium(0) complexes and, surprisingly, that 1:1 palladium(0) complexes of Xphos and Mor-Dalphos are unstable with respect to dissociation to free ligand and palladium metal. In other words, these two ligands and, by implication, other sterically demanding phosphine ligands do not form palladium(0) compounds.

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

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Several Pd(0) complexes catalyze the dimerization of Mes*PCNPh [2, Mes* = 2,4,6-(t-Bu)3C6H2] to the unsymmetrical heterocycle Mes*P(mu-CNPh)NPh(mu-CPMes*) (5). The symmetrical dimer [Mes*P(mu-CNPh)]2 (7), which forms slowly by uncatalyzed dimerization of 2, does not interconvert with 5; both 5 and 7 were structurally characterized by X-ray crystallography. The Pt complexes PtL2[eta2-(P,C)-Mes*PCNPh] [8, L = 1/2 dppe (Ph2PCH2-CH2PPh2); 9, L = PPh3; 10, L = PCy3 (Cy = c-C6H11)], models for intermediates in the catalysis, were prepared. Isomerization of Mes*PCCPh2 (3) to the phosphaindan [2,4-(t-Bu)2C6H2(G-CMe2CH 2PCH=CPh2)] (6), which we previously observed with Rh(I) catalysts, is catalyzed by Pt(PCy3)2 or the known Pt(PPh3)2[eta2-(P,C)-Mes*PCCPh2] (12). Comparison of the metal-mediated reactions of 2 and 3 suggests that the initial steps in the catalyses, coordination of the phosphacumulene to M(0), followed by loss of a ligand, are similar.

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

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Chloroacyl halides are obtained under mild conditions by catalytic carbonylation in halogenated solvents of allylic halides or ethylene and allyl chloride mixtures under pressure of CO and anhydrous HCl in the presence of PdCl2; excellent selectivities for dichloroacyl and chloroacyl derivatives are achieved. Allyl chloride is partly consumed for the regeneration of palladium chloride. The product of oxidative addition of HCl to the oligomeric [Pd(CO)Cl](n) formed in situ by reaction of CO on PdCl2 is proposed as the first step towards the generation of the active species.

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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 one-pot reaction that directly converts dihydrosilanes into silyl ethers of tertiary silanes is reported. Under palladium catalysis, one Si?H bond of the dihydrosilane formally engages in C(sp3)?Si bond formation with a vinyl iodide while the other Si?H bond is transformed into a silyl iodide that undergoes facile alcoholysis with an alcohol. The C?C double bond is reduced in that process. This three-component reaction provides in a single synthetic operation an access to silyl ethers of functionalized and hindered alcohols. Several of those would otherwise be difficult to make but the intermediacy of a highly reactive silyl iodide even allows for tert-butanol to react at room temperature.

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

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An efficient new formal insertion strategy via combination of reductive elimination and oxidative addition sequence was reported, in which the transient N-acyliminium ions formed via hydrocarbonylation function as key intermediates. This strategy has enabled a novel palladium-catalyzed hydrocarbonylative cyclization of azaarene-tethered alkenes or dienes via sequential insertion of a Ca? C bond, CO, and a Ca? N bond into palladium-hydride bonds. This method provides a new and highly efficient synthetic approach to quinolizinones and its derivatives with extended I-conjugated systems, possessing tunable emission wavelengths and good photoluminescence capabilities.

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