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By using Pd0/Mandyphos, we achieved a three-component aminoarylation of alkynes to generate enamines, which are then hydrolyzed to either alpha-arylphenones or alpha,alpha-diarylketones. This Pd-catalyzed method overcomes established known pathways to enable the use of amines as traceless directing groups for C?C bond formation.

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

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Functionalization of single-walled (SWCNTs) and double-walled carbon nanotubes (DWCNTs) with a charge stabilizing zinc porphyrin functionalized with triphenylamine entities has been accomplished. The synthetic approach involved the reaction of tris-(triphenylamine)porphyrinato zinc(ii) with iodobenzene functionalized nanotubes through a Sonogashira C-C cross coupling reaction under microwave irradiation conditions. Evidence of covalent functionalization and the extent of functionalization was obtained from systematic studies carried out by AFM, TGA, XPS and Raman spectroscopy techniques. The porphyrin-nanotube interactions in the SWCNT-porphyrin hybrid were probed by studies involving optical absorbance, Raman spectroscopy, steady-state and time resolved emission and electrochemical studies. The fluorescence of porphyrin in this hybrid was found to be quenched due to interactions with the CNTs. Femtosecond transient absorption spectral studies covering both the visible and near-infrared regions were supportive of excited state charge transfer interactions in the zinc porphyrin-SWCNT. The charge separated state was persistent for about 1 ns. Electron pooling experiments suggested that this donor-acceptor nanohybrid could be a useful photocatalyst.

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

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Compounds of the formula (I), or a pharmaceutically-acceptable salt, or an in-vivo-hydrolysable ester thereof, 1wherein, for example, X is ?O? or ?S?; HET is an optionally substituted C-linked 5-membered heteroaryl ring containing 2 to 4 heteroatoms independently selected from N, O and S; Q is selected from, for example, Q1 and Q2 2R2 and R3 are independently hydrogen or fluoro; T is selected from a range of groups, for example, an N-linked (fully unsaturated) 5-membered heteroaryl ring system or a group of formula (TC5): 3wherein Rc is, for example, R13CO?, R13SO2? or R13CS?; wherein R13 is, for example, optionally substituted (1-10C)alkyl or R14C(O)O(1-6C)alkyl wherein R14 is optionally substituted (1-10C)alkyl; are useful as antibacterial agents; and processes for their manufacture and pharmaceutical compositions containing them are described.

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

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Double-label crossover, modified substrate, and catalyst comparison experiments in the gold and palladium dual-catalytic rearrangement/cross- coupling of allenoates were performed in order to probe the mechanism of this reaction. The results are consistent with a cooperative catalysis mechanism whereby (1) gold activates the substrate prior to oxidative addition by palladium, (2) gold acts as a carbophilic rather than oxophilic Lewis acid, (3) competing olefin isomerization is avoided, (4) gold participates beyond the first turnover and therefore does not serve simply to generate the active palladium catalyst, and (5) single-electron transfer is not involved. These experiments further demonstrate that the cooperativity of both gold and palladium in the reaction is essential because significantly lower to zero conversion is achieved with either metal alone in comparison studies that examined multiple potential gold, palladium, and silver catalysts and precatalysts. Notably, employment of the optimized cocatalysts, PPh 3AuOTf and Pd2dba3, separately (i.e., only Au or only Pd) results in zero conversion to product at all monitored time points compared to quantitative conversion to product when both are present in cocatalytic reactions.

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

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Synthesis of benzofuran fused 1-azaazulene derivative (cyclohepta[d]benzo[4,5]furano[2,3-b]pyrrole) (4) was achieved successfully by tandem intermolecular Suzuki coupling/intramolecular Buchwald-Hartwig type coupling of 2-chloro-3-iodo-1-azaazulene with 2-hydroxyphenylboronic acid pinacolate in the presence of Pd catalyst. The compound 4 was also obtained by the reaction of 2-chloro-1-azaazulene with 2-iodophenol in the presence of Pd catalyst in one pot. It was considered that the obtained tetra-cyclic heterocycles would consist 18pi peripheral conjugated system by the studies of UV/Vis spectra and 1H NMR spectra, together with DFT calculation.

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

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Treatment of two equivalents of the triphosphenium zwitterion L with sources of Ni0 and Pd0 form the mononuclear eta2-diphosphoniodiphosphene complexes 1 and 2. The reaction between L and [FeCp(CO)2]2 results in the binuclear mu-eta1:eta1-diphosphoniodiphosphene iron complex 3, which features an alternative bonding motif of the diphosphoniodiphosphene unit. The formation of these species has been confirmed by spectroscopic methods and single-crystal X-ray diffraction analysis, and their electronic structures have been elucidated using computational methods.

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

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1,4,5,8,9,12-Hexaazatriphenylenes, 1,4,5,8-tetraazaphenanthrene, and quinoxalines, each with six, four, and two N,N-diphenylaminobiphenyl and N,N-diphenylaminophenyl groups, respectively, were prepared and their absorption and fluorescent spectral behaviors were investigated. These compounds showed strong fluorescent solvatochromism arising from the donor-acceptor nature of the pi-electron-deficient aromatic core and pi-electron-rich diphenylamino terminal 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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The subject matter herein is directed to carbazole-containing sulfonamide derivatives and pharmaceutically acceptable salts or hydrates thereof of structural formula I wherein the variable R1, R2, R3, R4, R5, R6, R7, A, B, C, D, E, F, G, H, a, and b are accordingly described. Also provided are pharmaceutical compositions comprising the compounds of formula I to treat a Cry-mediated disease or disorder, such as diabetes, obesity, metabolic syndrome, Cushing’s syndrome, and glaucoma.

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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 here an unprecedented palladium-catalysed O-allylation of alpha-hydroxyphosphonates. The method was eventually included in a sequential Pudovik/Tsuji-Trost type O-allylation/Ring-Closing Metathesis to afford a variety of phosphorylated heterocycles of various sizes ranging from 5 to 16 starting from readily available aldehydes. (Figure 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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The indium-mediated allylation of novel 3-(2-Boc-hydrazono)indolin-2-one derivatives, followed by a palladium-catalysed carboamination reaction, is described to afford unprecedented spirocyclic oxindoles in good yields. The method provides an efficient access to both cis and trans diastereoisomers of highly functionalized compounds, bearing an N-Boc, 5-substituted pyrazolidine ring at the C3-oxindole spiro junction. The versatility of the method is fully demonstrated starting from a series of substituted isatins and employing a variety of aryl halides in the key cyclization step.

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