A new application about Bis(dibenzylideneacetone)palladium

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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

Some scientific research about Bis(dibenzylideneacetone)palladium

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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

Final Thoughts on Chemistry for Bis(tri-tert-butylphosphine)palladium

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The sodium salts of allyldimethylsilanol and 2-butenyldimethylsilanol undergo palladium-catalyzed cross-coupling with a wide variety of aryl bromides to afford allylated and crotylated arenes. The coupling of both silanolates required extensive optimization to deliver the expected products in high yields. The reaction of the allyldimethylsilanolate takes place at 85C in 1,2-dimethoxyethane with allylpalladium chloride dimer (2.5 mol %) to afford 73-95% yields of the allylation products. Both electron-rich and sterically hindered bromides reacted smoothly, whereas electron-poor bromides cross-coupled in poor yield because of a secondary isomerization to the 1-propenyl isomer (and subsequent polymerization). The 2-butenyldimethylsilanolate (E/Z, 80:20) required additional optimization to maximize the formation of the branched (gamma-substitution) product. A remarkable influence of added alkenes (dibenzylideneacetone and norbornadiene) led to good selectivities for electron-rich and electron-poor bromides in 40-83% yields. However, bromides containing coordinating groups (particularly in the ortho position) gave lower, and in one case even reversed, selectivity. Configurationally homogeneous (E)-silanolates gave slightly higher gamma-selectivity than the pure (Z)-silanolates. A unified mechanistic picture involving initial gamma-transmetalation followed by direct reductive elimination or sigma-pi isomerization can rationalize all of the observed trends.

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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

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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

Discovery of Bis(tri-tert-butylphosphine)palladium

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Some norbenzomorphans exhibit high affinity for sigma 1 and sigma 2 receptors, and varying the position of substituents on the aromatic ring of this scaffold has a significant effect on subtype selectivity. In particular, compounds bearing several different substituents at C7 of the norbenzomorphan ring system exhibit a general preference for the sigma 1 receptor, whereas the corresponding C8-substituted analogues preferentially bind at the sigma 2 receptor. These findings suggest that the norbenzomorphan scaffold may be a unique chemical template that can be easily tuned to prepare small molecules for use as tool compounds to study the specific biological effects arising from preferential binding at either sigma receptor subtype. In the absence of structural characterization data for the sigma 2 receptor, such compounds will be useful toward refining the pharmacophore model of its binding site.

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