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The first catalytic asymmetric dearomative [3 + 2] cycloaddition of 3-nitroindoles with vinylcyclopropanes has been established, which constructed chiral cyclopenta[b]indoline scaffolds in generally high enantioselectivities (up to 97% ee). This reaction also represents the first application of all-carbon 1,3-dipoles in catalytic asymmetric dearomative [3 + 2] cycloadditions of 3-nitroindoles. This approach will not only advance the catalytic asymmetric dearomatization reactions of electron-deficient indoles but also provide an efficient method for constructing chiral cyclopenta[b]indoline scaffolds.

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

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Complex 1b shows an unprecedented high activity in the Heck reaction. Kinetic studies show that in this system not the oxidative addition but the alkene coordination/migratory insertion is the rate determining step.

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

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Oxidative addition of N-(2-iodophenyl)formamide to Pd(dba)2 (dba = dibenzylideneacetone) in the presence of 4,4?-ditertbutyl-2,2?-bipyridine (tBubpy) produces [Pd(C6H4NHCHO-2)I(tBubpy)] (1) which inserts 2-iodophenyl isocyanide to give [Pd{C(NC6H4I-2)C6H4NHCHO-2}I(tBubpy)] (2). Dehydroiodination of 2 with Tl(acac) (acacH = acetylacetone) gives the stable Pd(iv) complex OC-6-35-[Pd{C,N,N-C(NC6H4-2)C6H4NCHO-2}I(tBubpy)] (4) likely resulting from the spontaneous oxidative addition of the I-Ar moiety present in the unstable intermediate Pd(ii) complex [Pd{C,N-C(NC6H4I-2)C6H4NCHO-2}(tBubpy)] (3). The crystal structure of 4 shows various C-H?O hydrogen bonds resulting in chains of dimers stacked along the a axis.

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

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Commercial Pdx(dba)y from various suppliers was found to vary considerably in appearance, homogeneity, purity, and catalytic activity. The Buchwald-Hartwig amination of 4-bromoanisole (5) with aniline (6) was established as a sensitive test reaction to probe the efficiency of Pdx(dba)y batches in catalytic transformations. The yields obtained with 17 different Pdx(dba)y batches ranged from 10% to nearly quantitative and could not be predicted reliably on the basis of any physical or spectroscopic descriptor alone. The best results in the catalytic test reaction were consistently achieved with a self-made slowly crystallized Pd2(dba)3·toluene adduct. A protocol is disclosed that allows batches of Pdx(dba)y with unsatisfactory or inconsistent performance to be converted into this reliable precatalyst.

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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 linear tetraphosphine containing a PNP phosphazane bridge, rac-bis[(diphenylphosphinomethyl)phenylphosphino]phenylamine (rac-dpmppan), was synthesized and utilized to support a series of Pd/Pt mixed metal tetranuclear chains, [Pd4?nPtn(mu-rac-dpmppan)2(XylNC)2](PF6)2 (XylNC=xylyl isocyanide; n=0: Pd4 (1), 1: PtPd3 (2), 2: PtPd2Pt (3), 2: Pt2Pd2 (4), 3: Pt2PdPt (5)), in which the number and positions of additional Pt atoms were successfully controlled depending on the respective synthetic procedures using transformations from 1 to 3 through 2 and from 4 to 5 by redox-coupled exchange reactions. The 31P{1H} NMR and ESI mass spectra and X-ray diffraction analyses revealed almost identical tetranuclear structures, with slight contraction of metal-metal bonds according to incorporation of Pt atoms. The electronic absorption spectra of 1?5 exhibited characteristic bands at 635?510 nm with an energy propensity depending on the number and positions of Pt centres, which were assigned to HOMO (dsigma*sigmasigma*) to LUMO (dsigma*sigma*sigma*) transition by theoretical calculations. The present results demonstrated that the electronic structures of Pd/Pt mixed-metal tetranuclear complexes are finely tuned as orbital-overlapping alloyed metal chains by atomically precise Pt incorporation in the Pd4 chain.

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

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Bimetallic Pd/Cu and Pd/Ag catalytic systems were used for borylation of propargylic alcohol derivatives. The substrate scope includes even terminal alkynes. The reactions proceed stererospecifically with formal S N2? pathways to give allenyl boronates. Opening of propargyl epoxides leads to 1,2-diborylated butadienes probably via en allenylboronate intermediate.

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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, 32005-36-0, name is Bis(dibenzylideneacetone)palladium, introducing its new discovery. Formula: C34H28O2Pd

A novel and unusual palladium-catalyzed [4+2] annulation of cyclopropenes with benzosilacyclobutanes is reported. This reaction occurred through chemoselective Si?C(sp2) bond activation in synergy with ring expansion/insertion of cyclopropenes to form new C(sp2)?C(sp3) and Si?C(sp3) bonds. An array of previously elusive bicyclic skeleton with high strain, silabicyclo[4.1.0]heptanes, were formed in good yields with excellent diastereoselectivity under mild conditions. An asymmetric version of the reaction with a chiral phosphoramidite ligand furnished a variety of chiral bicyclic silaheterocycle derivatives with good enantioselectivity (up to 95.5:4.5 er). Owing to the mild reaction conditions, the good stereoselectivity profile, and the ready availability of the functionalized precursors, this process constitutes a useful and straightforward strategy for the synthesis of densely functionalized silacycles.

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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 palladium-catalyzed heck-type cascade cyclization of (Z)-1-iodo-1,6-dienes with N-tosyl hydrazones is reported. The alkylpalladium intermediate coupled with the diazo compound, generating the second alkylpalladium species bearing two beta-H, which generated a terminal alkene as the major products in the anti-Zaitsev way via the highly regioselective beta-H elimination. It provided a new way to synthesize tetrahydropyridine derivatives bearing a terminal alkene.

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

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Asymmetric synthesis of chiral allenes starting from prochiral substrates under mild reaction conditions promoted by Pd-SYNPHOS catalyst is reported. This protocol provides an efficient access to various enantioenriched aryl- and alkyl- substituted allenes, which are versatile building blocks of high utility to both organic and medicinal chemists, in excellent isolated yields (up to 96%) and high enatiomeric ratio values (up to 95:5). In addition, a comparative study using several C2-symmetric atropisomeric diphosphine ligands revealed the overwhelming impact of the steric and electronic properties of the ligands for the catalytic efficiency of this process.

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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 report a series of arylpalladium complexes of acetamidate, sulfonamidate, and deprotonated oxazolidinone ligands that undergo reductive elimination with rates and yields that depend on the binding mode of the ancillary and amidate ligands. Complexes of the acetamidate ligands containing the bidentate phosphines DPPF and Xantphos as ancillary ligands undergo reductive elimination. The rate and yield were higher from the complex ligated by Xantphos, which contains a larger bite angle. In contrast, the analogous amidate complex containing a single sterically hindered monodentate ligand and a kappa2-bound amidate ligand does not undergo reductive elimination. This trend of faster reductive elimination from complexes containing bidentate ancillary ligands than from a complex with a single monodentate ancillary ligand is unusual and is consistent with an effect of the denticity of the ancillary ligand on the binding mode of the amidate. Complexes of sulfonamidate ligands underwent reductive elimination faster than complexes of acetamidates, and reductive elimination occurred from complexes containing both bidentate and monodentate ancillary ligands. Like reductive elimination from the acetamidate complexes, reductive eliminations from the sulfonamidate complexes were faster when the complexes possessed bidentate Xantphos and kappa1-sulfonamidate ligands. Copyright

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