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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

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The bis(tri-tert-butylphosphine)palladium(0) [Pd(tBu3P)2]-catalyzed synthesis of fluorinated closo-carboranes from 3D aromatic iodo-closo-carboranes by nucleophilic halogen exchange using silver(I) fluoride is described. Fluorination of 2-iodo-closo-p-carborane proceeded more readily than that of 9-iodo-closo-m-carborane. Iodine?fluorine exchange at 9-iodo-closo-o-carborane was not successful yielding instead a charge-compensated dibutylphosphonio nido-o-carborane. The described methodology advances the understanding of nucleophilic fluorination at aromatic systems by Pd0/PdII catalysis. With further optimization, it could find application in the synthesis of 18F-labeled carboranyl diagnostics for biomedical applications.

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

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Bis-doenes 4 react with distannanes 1, disilanes 2, and silylstannanes 3 in the presence of a catalytic amount of a palladium complex to afford carbocyclization-distannylation, -disilylation and -silastannylation products in high yields.Reaction of distannanes 1a, b with bis-dienes 4a, b as well as reaction of disilane 2b with bis-diene 4d proceeded regio- and stereo-selectively to afford a single product: trans-(E),(Z) isomers.Regio and stereo-selective reaction was also realized with the disilane 2b and bis-diene 4e to provide only trans-(E),(E) isomer.In other cases, the reactions proceeded regioselectively, but the stereoselectivity was modest.The X-ray crystal structures of the cyclopropanes 10 and 11 have been determined.

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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 synthesis of a bis-silylated 15-membered azatriolefinic macrocycle is described as well as its co-gelification with tetraethyl orthosilicate. The resulting material was treated with Pd(dba)2 affording an hybrid organic-inorganic material containing macrocyclic palladium(0) complex covalently bonded to the silica matrix. The activity of this material as catalyst or precatalyst in Suzuki cross-coupling and telomerization of butadiene with methanol and phenol is presented.

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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 xanthene-based bismuthane/phosphane chelating ligand has been accessed that has enabled the synthesis of a palladium(0) bismuthane complex. The bismuthane donor proved to be hemilabile as it switched to a dangling position upon addition of O2 that gave a palladium(II) peroxide complex. Unlike the corresponding 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) palladium peroxide, the bismuth analogue could be employed for catalytic phosphane oxidation and oxidative phenol coupling.

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

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Intermetallic compounds are atomically ordered inorganic materials containing two or more transition metals and main-group elements in unique crystal structures. Intermetallics based on group 10 and group 14 metals have shown enhanced activity, selectivity, and durability in comparison to simple metals and alloys in many catalytic reactions. While high-temperature solid-state methods to prepare intermetallic compounds exist, softer synthetic methods can provide key advantages, such as enabling the preparation of metastable phases or of smaller particles with increased surface areas for catalysis. Here, we study a generalized family of heterobimetallic precursors to binary intermetallics, each containing a group 10 metal and a group 14 tetrel bonded together and supported by pincer-like pyridine-2-thiolate ligands. Upon thermal decomposition, these heterobimetallic complexes form 10-14 binary intermetallic nanocrystals. Experiments and density functional theory (DFT) computations help in better understanding the reactivity of these precursors toward the synthesis of specific intermetallic binary phases. Using Pd2Sn as an example, we demonstrate that nanoparticles made in this way can act as uniquely selective catalysts for the reduction of nitroarenes to azoxyarenes, which highlights the utility of the intermetallics made by our method. Employing heterobimetallic pincer complexes as precursors toward binary nanocrystals and other metal-rich intermetallics provides opportunities to explore the fundamental chemistry and applications of these materials.

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

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Red fluorescent dyes bis(4-(N-(9,9-diethyl-2-fluorenyl)phenylamino)phenyl) fumaronitrile (EFPAFN) and bis(4-(N-(9-phenanthryl)-3,5-dimethylphenylamino) phenyl)fumaronitrile (PhMPAFN), blue fluorescent dyes 2,7-bis(N-2-(9,9- diethylfluorenyl) phenylamino)-9,9-diethylfluorene (EFPAEF) and 2,7-bis(N-9-phenanthryl-3,5-dimethylphenylamino)-9,9-diethylfluorene (PhMPAEF) were prepared. The red dyes with donor-acceptor structure showed strong red photoluminescence at 676 and 650 nm in evaporated film. The five non-doped red devices showed emission at 680, 676, 680, 692 and 656 nm with efficiencies of 2.93, 1.33, 2.58, 2.96 and 1.04 cd/A. The three non-doped green and three blue devices emitted EL peaks at 516, 532, 420, 424, 457 and 520 nm with maximum efficiencies of 0.33, 0.55, 0.45, 1.25, 0.43, and 0.45 cd/A, respectively. The three blue devices exhibited narrower full width at half maximum of 42, 49 and 84 nm. EFPAFN, EFPAEF, PhMPAFN and PhMPAEF were multifunctional compounds as emitters and hole-transporting materials, device efficiencies kept relatively small decline within a wide range of current density. Fumaronitrile or fluorene bridge with the same non-planar fluorenyl or phenanthryl amino unit and the different device fabrications achieved non-doped red-green-blue (R-G-B) EL emissions.

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

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Arenediazonium tetrafluoroborates (ArN2BF4 where Ar = Ph, 4-MeC6H4, 4-BrC6H4, 4-IC6H4 and 4-NO2C6H4) reacted easily with CH2=CHSiMe3 at 25 deg C to give ArCH=CH2, (E)-ArCH=CHSiMe3 and Ar(Me3Si)C=CH2 in excellent yields under palladium(0) catalysis. (E)-ArCH=CHSiMe3 compounds were obtained predominantly and isolated in good yields by using an excess of CH2=CHSiMe3 over ArN2BF4.Protodesilylation of the reaction mixture afforded styrene derivatives.

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