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A direct and facile palladium-catalyzed C-H bond oxidative carbonylation reaction and oxidative cyclization for the synthesis of polycyclic aromatic hydrocarbons (PAHs) is reported herein. The intramolecular cyclocarbonylation, through C-H activation and C-C, C-O bond formations under mild conditions, proceeds smoothly with good functional group tolerance in high to excellent yields. The intramolecular palladium-catalyzed direct oxidative C-H bond functionalization for the C-O bond formation is also demonstrated, which provides an efficient approach for the construction of various PAHs.

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

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Luminescent materials with red emission are promising materials for optoelectronic devices and biological sciences. However, their synthesis is often complicated. In this work, we developed a facile approach to generating red-emissive luminogens with aggregation-induced emission (AIE) characteristics from commercially available reactants. The new compounds, abbreviated PN-BTZ-Cz and DP-BTZ-Cz, were prepared by coupling 4,7-dibromobenzo[c][1,2,5]thiadiazole with (1-naphehyl)phenylamine or diphenylamine followed by the reaction of the monobromo-substituted compounds with carbazole. Although all of the reactants were non-AIE-active, PN-BTZ-Cz and DP-BTZ-Cz showed AIE characteristics. This suggested that the AIE chromophores were generated in situ through the reactions. PN-BTZ-Cz and DP-BTZ-Cz were soluble in common organic solvents and showed red emission with high fluorescence quantum yields of 42.2 and 38.3% in the film, respectively. They were thermally and morphologically stable, as revealed by their high decomposition temperature (up to 327 C) and glass-transition temperature (up to 120 C). Nondoped organic light-emitting diodes with a configuration of ITO/HATCN/TAPC/PN-BTZ-Cz or DP-BTZ-Cz/Bphen/Liq/Al were fabricated using these compounds as emitting layers, which emitted red electroluminescence at a low turn-on voltage (down to 2.8 V) with a maximum external quantum yield of up to 2.7% and a small efficiency roll-off.

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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 Tsuji?Trost allylation of CH acids, in particular, those of the YCH2CO2Et type (Y = CO2Et, C(O)Me, CN), with allylic acetates in the K2CO3?DMF system in the presence of palladium catalysts with ligands RN(PPh2)2 (R = Ph, Pri, c-C6H11) is accomplished.

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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 herein the preparation, the electrochemical, the absorption and the emission properties of a new heteroleptic bisterpyridine ruthenium complex. The first terpyridine is functionalized, on the 4? position, by a phosphonic acid group and the second terpyridine bears in the 4? position a tert-thiophenyl unit attached via an ethanyl spacer. The latter complex was tested in dye-sensitized solar cells using the liquid electrolyte (I2/LiI/tert-butylpyridine/propylene carbonate) or the solid poly(3-octylthiophene) as a hole conductor. It displays an improved photovoltaic photoconversion efficiency compared to the analogous complex in which the tert-thiophene is directly linked to the terpyridine ligand. This study shows that the covalent attachment of a thiophene residue on the sensitizer is a promising strategy for the development of solid-state dye-sensitized solar cells and it highlights the benefit of introducing a non-conjugated spacer between the thiophenyl unit and the polypyridine ruthenium sensitizer.

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

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An enantioselective and branch-regioselective alpha-allylation of N-methyl anilines under dual palladium/photoredox catalysis is described. Readily available N-methyl anilines are used as formal “hard” alkyl nucleophiles without preactivation. Acetic acid is the only side product, which leads to a high atom economy of this reaction. This protocol shows good functional group tolerance and broad scope. A range of chiral homoallylic amines were prepared in moderate to good yields (up to 76%) and excellent regioselectivities (B:L > 95:5 in all cases) and enantioselectivities (up to 96% ee) under mild reaction conditions.

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

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Pd-catalyzed cross-coupling of halides with CF3-substituted diazo compounds or N-tosylhydrazones has been explored for the synthesis of CF3-substituted alkenes and 1,3-butadienes. Pd-carbene migratory insertion plays the key role in these transformations. 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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A convergent procedure has been developed for the preparation of fac-tris(2-phenylpyridyl)iridium(III) cored dendrimers with first- and second-generation dendrons that each contain one and two carbazole units, respectively. The carbazole moieties are both an electroactive moiety and a branching unit in the dendron. The photoluminescence quantum yields of neat films of the first- and second-generation dendrimers were 48 ± 5% and 39 ± 4%, respectively. These values are substantially higher than for equivalent first- and second-generation dendrimers with phenyl moieties at the branching points of the dendrons instead of the carbazole units. The improved solid state luminescent properties can be attributed to the increased steric demand of the carbazole unit relative to the phenyl ring, which reduces more effectively the intermolecular interactions that cause the cores to be less emissive. Electrochemical experiments showed that both the core of the dendrimers and the dendrons were electroactive. Thin film hole mobilities of the first-generation dendrimer with the carbazolyl branching units in the dendrons were found to be higher than the equivalent dendrimer with biphenyl branching units across a range of fields.

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

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Despite recent advances, a general method for the synthesis of alpha-carbonyl-alpha?-(hetero)aryl sulfoxonium ylides is needed to benefit more greatly from the potential safety advantages offered by these compounds over the parent diazo compounds. Herein, we report the palladium-catalyzed cross-coupling of aryl bromides and triflates with alpha-carbonyl sulfoxonium ylides. We also report the use of this method for the modification of an active pharmaceutical ingredient and for the synthesis of a key precursor of antagonists of the neurokinin-1 receptor. In addition, the mechanism of the reaction was inferred from several observations. Thus, the oxidative addition complex [(XPhos)PhPdBr] and its dimer were observed by 31P{1H} NMR, and these complexes were shown to be catalytically and kinetically competent. Moreover, a complex resulting from the transmetalation of [(XPhos)ArPdBr] (Ar = p-CF3-C6H4) with a model sulfoxonium ylide was observed by mass spectrometry. Finally, the partial rate law suggests that the transmetalation and the subsequent deprotonation are rate-determining in the catalytic cycle.

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

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Since the 1970s, palladium-catalysed carbon?carbon (C?C) bond formation has made a critical impact in organic synthesis. In early studies, homogeneous palladium catalysts were extensively used for this reaction with limitations such as difficulty in separation and recycling ability. Lately, heterogeneous palladium-based catalysts have shown promise as surrogates for conventional homogeneous catalysts in C?C coupling reactions, since the product is easy to isolate, while the catalyst is reusable and hence sustainable. Recently, a better part of these heterogeneous palladium catalysts are supported on carbon nanotubes (Pd/CNTs), that have shown superior catalytic performance and better recyclability since the CNT support imparts stability to the palladium catalyst. This review discusses the wide variety of surface functionalization techniques for CNTs that improve their properties as catalyst supports, as well as the methods available for loading the catalyst nanoparticles onto the CNTs. It will survey the literature where Pd/CNTs catalysts have been utilized for C?C coupling reactions, with particular emphasis on Suzuki?Miyaura and Mizoroki?Heck coupling reactions. It will also highlight some of the important parameters that affect these 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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The two types of conjugated polymers were synthesized with boron pyridinoiminate with or without the fused structure in the ligand moiety. From optical measurements, it was shown that the polymer involving the fused complex had intense luminescent property only in the solution state. In contrast, another polymer presented similar emission intensities both in the solution and film states. By introducing the simple ring fuse structure, solution and solid-state luminescent properties of conjugated polymer can be tuned. Finally, the aggregation-caused quenching-resistant luminescent polymer can be produced.

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