Simple exploration of Bis(dibenzylideneacetone)palladium

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(Chemical Equation Presented) Two are better than one: Mixed lithium-magnesium complexes of the type R2NMgCl·LiCl are kinetically highly active bases that convert a range of polyfunctional aromatic and heteroaromatic substrates into the corresponding magnesiated derivatives with high regioselectivity.

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

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Inspired by the proclivity of various palladium sources to form nanoparticles in imidazolium-based ionic liquids, we now report that tris-imidazolium salts bearing hexadecyl chains and a bridging mesitylene moiety are potent stabilizers of palladium nanoparticles efficiently prepared via a Chaudret-type hydrogenation of the bis(dibenzylideneacetone)palladium(0). The palladium nanoparticles have been isolated in pure form and characterized by 1H nuclear magnetic resonance, transmission electron microscopy, electron diffraction and dynamic light scattering. The new materials proved effective in Suzuki cross-coupling at a loading of 0.2% palladium. Thus, using a tris-imidazolium iodide-palladium material, a series of biaryl products has been prepared starting from aryl bromides and some activated chlorides. The possibility that this catalytic activity might be due to the formation of palladium N-heterocyclic carbenes has been addressed through solid state 13C NMR and the synthesis of an imidazolium analogue in which the acidic 2-H was replaced with a methyl group. 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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The transition-metal-catalyzed alpha-arylation of carbonyl compounds is a widely practiced method for C-C bond formation. Several enantioselective versions of this process have been reported, but intermolecular, enantioselective coupling reactions of aryl electrophiles with alpha-fluoro carbonyl compounds have yet to be disclosed. We report enantioselective coupling of aryl and heteroaryl bromides and triflates with alpha-fluoroindanones catalyzed by palladium complexes of a BINOL-derived monophosphine and Segphos, respectively. The enolates were generated directly from alpha-fluoroindanones in the presence of potassium phosphate base during the reactions. We also report that reactions of alpha-fluorotetralones occur in high yields and enantioselectivities when conducted with enolates generated by elimination of trifluoroacetate from trifluoromethyl beta-diketone hydrates. These reactions were catalyzed by palladium complexes of the commercially available bisphosphine Difluorphos. Thus, the formation of enantioenriched alpha-aryl-alpha-fluoroketones can be readily achieved by C-C bond formation when the appropriate palladium catalyst and alpha-fluoro enolate precursor were used.

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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 nickel(II) and palladium(II) aryl complexes substituted in the ortho position of the aromatic ring by a (pinacolato)boronic ester group, [MBr{o-C6H4B(pin)}L2] (M = Ni, L2 = 2PPh3 (2a), 2PCy3 (2b), 2PEt3 (2c), dcpe (2d), dppe (2e), and dppb (2f); M = Pd, L2 = 2PPh3 (3a), 2PCy3 (3b), and dcpe (3d)), has been prepared. Many of these complexes react readily with KOtBu to form the corresponding benzyne complexes [M(eta2-C6H4)L2] (M = Ni, L2 = 2PPh3 (4a), 2PCY3 (4b), 2PEt3 (4c), dcpe (4d); M = Pd, L2 = 2PCy3 (5b)). This reaction can be regarded as an intramolecular version of a Suzuki cross-coupling reaction, the driving force for which may be the steric interaction between the boronic ester group and the phosphine ligands present in the precursors 2 and 3. Complex 3d also reacts with KOtBu, but in this case disproportionation of the initially formed eta2-C6H4 complex (5d) leads to a 1:1 mixture of a novel dinuclear palladium(I) complex, [(dcpe)Pd(mu2-C6H4)Pd(dcpe)] (6), and a 2,2?-biphenyldiyl complex, [Pd(2,2?-C6H4C6H4)-(dcpe)] (7d). Complexes 2a, 3b, 3d, 4b, 5b, 6, and 7d have been structurally characterized by X-ray diffraction; complex 5b is the first example of an isolated benzyne-palladium(0) 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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Neutral compounds of the type [MX2(L)] and [MX(Me)(L)] and ionic complexes of the type [M(Me)(L)](O3SCF3), in which X = Cl, Br, I; M = Pd, Pt; L = 2-(diphenylphosphino)-benzylidene-S(-)-alpha-methyl-benzylamine, have been prepared and characterized. Single crystal X-ray determinations of [PdCl2(L)] (1a) and [PtI2(L)] (3b) showed, in both cases, a chelate coordination of the PN ligand thereby forming a six-membered ring. The square planar surrounding is completed by the two halide atoms. The single crystal X-ray determination of [PdCl(Me)Cl(L)] (4a) shows an analogous geometry with a chelating PN ligand, a chloride atom and a methyl group, which is positioned cis to the phosphorus atom, completes the square planar surrounding. The methylpalladium and -platinum complexes reacted with CO to give the corresponding acetyl complexes. The insertion rates increased in the order Cl < Br < O3SCF3- while the reaction is first order in metal complex and first order in CO concentration. Complexes [Pd(eta3-allyl)(PN)]+Y- (Y = C1, O3SCF3) with symmetric allyl groups 2-RC3H5 (R = Me, C(O)Me), 2-MeC3Me4 and asymmetrically substituted allyl groups 2-R-C3H2Me2 (R = H, Me) have been prepared. Temperature dependent 1H, 31P{1H} and 13C{1H} NMR has been used to determine the influence of the chiral ligand on the structural aspects and dynamic features. It is shown that a delicate balance between counteracting steric and electronic factors determines the type of isomer, i.e. with the P atom cis or trans to the CMe2 moiety of the asymmetric allyl group. If you are interested in 32005-36-0, you can contact me at any time and look forward to more communication. Computed Properties of C34H28O2Pd

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

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Highly substituted alkenylsilanols (1), readily prepared from commercially available simple starting materials, are efficiently coupled with aryl or alkenyl halides in the presence of tetrabutylammonium fluoride (TBAF) and a palladium(0) catalyst. Yields are generally high and the reactions are highly stereoselective and compatible with a wide range of functional groups.

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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 protocol for palladium-catalyzed dearomative functionalization of simple, nonactivated arenes with Grignard reagents has been established. This one-pot method features a visible-light-mediated [4+2] cycloaddition between an arene and an arenophile, and subsequent palladium-catalyzed allylic substitution of the resulting cycloadduct with a Grignard reagent. A variety of arenes and Grignard reagents can participate in this process, forming carboaminated products with exclusive syn-1,4-selectivity. Moreover, the dearomatized products are amenable to further elaborations, providing functionalized alicyclic motifs and pharmacophores. For example, naphthalene was converted into sertraline, one of the most prescribed antidepressants, in only four operations. Finally, this process could also be conducted in an enantioselective fashion, as demonstrated with the desymmetrization of naphthalene.

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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 first high-yielding route to arylated 2H-pyrroles was developed. The methodology utilizes 2,5-disubstituted pyrroles that are metalated, and the aryl substituents are introduced by a palladium-catalyzed cross-coupling reaction. The prepared pyrroles can be rearranged to 2,3,5-trisubstituted pyrroles under acidic conditions. Attempts to convert the 2,3,5-trisubstituted pyrroles to 2,3,4,5-tetrasubstituted pyrroles by the dearomatization rearrangement strategy 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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A highly chemoselective intermolecular [2+2+2] cycloaddition of 2eq. of terminal alkynes with dimethyl acetylenedicarboxylate, which enables the straightforward synthesis of dialkylated o-phthalates, was successfully accomplished using a ruthenium catalyst, Cp*RuCl(cod) (Cp*: pentamethylcyclopentadienyl, cod: 1,5-cyclooctadiene). The co- cyclotrimerisation of alkynes and acetylenedicarboxylates usually affords 1:2 adducts (1,2,3,4-benzenetetracarboxylates), however, in the present reaction 2: 1 adducts (o-phthalates) are the major products unprecedentedly.

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

Simple exploration of Bis(dibenzylideneacetone)palladium

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The new palladacyclopropa[60]fullerene complexes incorporating alpha-keto stabilized phosphorus ylides were synthesized in a three-component reaction of the unsymmetrical phosphorus ylides [Ph2P(CH2)nPPh2C(H)C(O)C6H4-m-R] (n = 1, R = Br, NO2, (Y1, Y2); n = 2, R = Br, NO2, (Y3, Y4)), C60 and Pd(dba)2 (dba = dibenzylideneacetone). The obtained novel P,C-chelated [(eta2-C60)Pd(kappa2-Y1)] (1) and [(eta2-C60)Pd(kappa2-Y2)] (2) complexes and P,P-coordinated [(eta2-C60)Pd(Y3)2] (3) and [(eta2-C60)Pd(Y4)2] (4) complexes were characterized successfully by IR, UV-Vis, ESI-MS and NMR (1H, 13C and 31P) spectroscopic methods. Complexes 1-4 are rare examples of palladacyclopropa[60]fullerene complexes with phosphorus ylide ligands. Spectroscopic results revealed that none of possible side products including P,P-coordinated [(eta2-C60)Pd(Y1)2] and [(eta2-C60)Pd(Y2)2] complexes and also P,C-chelated [(eta2-C60)Pd(kappa2-Y3)] and [(eta2-C60)Pd(kappa2-Y4)] complexes are formed. The EDA analysis indicated that in all the above complexes the metal-ligand bonds are mostly electrostatic in nature.

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