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Palladium-catalysed cross-coupling of secondary C(sp3) organometallic reagents has been a long-standing challenge in organic synthesis, due to the problems associated with undesired isomerisation or the formation of reduction products. Based on our recently developed catalytic C-C bond formation with organolithium reagents, herein we present a Pd-catalysed cross-coupling of secondary alkyllithium reagents with aryl and alkenyl bromides. The reaction proceeds at room temperature and on short timescales with high selectivity and yields. This methodology is also applicable to hindered aryl bromides, which are a major challenge in the field of metal catalysed cross-coupling 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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Novel phosphorescent metal complexes containing 2-phenylisoquinoline ligands with at least two substituents on the isoquinoline ring are provided. The disclosed compounds have low sublimation temperatures that allow for ease of purification and fabrication into a variety of OLED devices.

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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 cyclobutanation of aryl sulfonates with strained alkenes has been developed. The methodology is featured to achieve the cleavage of both C-O and C-H bonds of phenol derivatives in one pot. Under the reaction conditions, in addition to reactive triflates, the relatively inactive tosylates and mesylates can also be transformed into the corresponding benzocyclobutanes in high yields. This reaction can be carried out in gram-scale experiments with a low loading of the palladium catalyst and is applicable to the cyclobutanative modification of bioactive molecules, highlighting its synthetic value in organic synthesis.

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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 invention relates to new amino-indole-substituted imidazolyl-pyrimidines of formula 1 wherein R1, R2, R3, R4 and R5 are defined as in claim 1 and pharmaceutically acceptable salts thereof and the use of these compounds for the preparation of a medicament for treating a disease selected from asthma, COPD, rheumatoid arthritis, specific lymphomas and specific diseases of the nervous system.

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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 catalytic stereoconvergent construction of vicinal all-carbon quaternary centers via double stereoablative enantioselective alkylation of a mixture having racemic and meso diastereomers of esters to afford exceptional levels of diastereo- (up to 17:1) and enantioselectivity (up to >99% ee). The strategy offers an efficient and general approach to dimeric cyclotryptamine alkaloids sharing a labile C3a-C3a? sigma-bond in the hexahydropyrroloindoline core.

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

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Over the last half-century, the molecular imaging technique of positron emission tomography (PET) has emerged as an important tool for biomedical research, drug development and medical diagnosis. The power of PET derives from its utilization of radiotracers that can report specific information on pharmacology, biochemistry, and physiology. Many of these radiotracers are heterocycles that have been labeled with a short-lived cyclotron-produced radioisotope, either carbon-11 (t1/2 = 20.4 min) or fluorine-18 (t1/2 = 109.8 min). This review addresses the chemical challenges to be met in producing PET radiotracers with these radioisotope labels at heterocyclic moieties and the methods now available for doing so.

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

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Two kinds of A1-(D-A2)3-type (A1, A2: acceptor, D: donor) triazine-based star-shaped acceptors, TzTPT-INCN and TzCDT-INCN, are reported to show strong face-on orientation with J- to H-type packing structural transformation with thermal annealing (TA) treatments. TA of the thin films of both acceptors mainly leads to the formation of thermodynamically more stable H-type packing with enhanced hypsochromic absorption peaks in the UV?vis spectra. The results agree well with calculations based on time-dependent density-functional theory. To determine the optimum TA conditions for fabricating organic photovoltaic (OPV) devices, in-depth studies are conducted through in situ grazing incidence wide-angle X-ray scattering to analyze changes in the molecular packing structure with respect to the TA temperature employed. Sequential deposition bilayer OPV devices are fabricated by combining the two acceptors with a donor polymer PBDB-T. Although the electron mobilities and power conversion efficiencies are improved slightly (PBDB-T/TzTPT-INCN: 4.26 to 4.65%, PBDB-T/TzCDT-INCN: 6.58 to 7.18%) via transformation from a J-dominant to H-dominant morphology, the differences are not significant. Similar charge transport characteristics are observed for both the H- and J-type stacked structures. The study can be used to better understand the modification of molecular packing via the manipulation of molecular design and to determine the correlation between packing structures and electrical properties.

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

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Kinetic, spectroscopic and computational studies examining a palladium-catalyzed imidoylative coupling highlight the dual role of isocyanides as both substrates and ligands for this class of transformations. The synthesis of secondary amides from aryl halides and water is presented as a case study. The kinetics of the oxidative addition of ArI with RNC-ligated Pd0species have been studied and the resulting imidoyl complex [(ArC=NR)Pd(CNR)2I] (Ar=4-F-C6H4, R=tBu) has been isolated and characterized by X-ray diffraction. The unprecedented ability of this RNC-ligated imidoyl-Pd complex to undergo reductive elimination at room temperature to give the amide in the presence of water and an F?/HF buffer is demonstrated. Its behavior in solution has also been characterized, revealing an unexpected strong tendency to give cationic complexes, and notably [(ArC=NR)Pd(CNR)3]+with excess isocyanide and [(ArC=NR)Pd(PP)(CNR)]+with bidentate phosphines (PP). These species may be responsible for catalyst deactivation and side-reactions. Ab initio calculations performed at the DFT level allowed us to rationalize the multiple roles of RNC in the different steps of 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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The divergent synthesis of star-shaped oligophenylene dendrimers is described. These latter consist of a triptycene central core decorated with various peripheral tetra- and octa-arylamine derivatives. The target compounds were prepared via a convenient [4 + 2] Diels?Alder cycloaddition reaction followed by palladium-catalyzed Buchwald?Hartwig Cross-Coupling reactions in very good overall yields. The dendritic structures were confirmed by 1H- and 13C-nuclear magnetic resonance, high resolution mass spectrometry, and thermogravimetric analysis. Photophysical studies of these star-shaped dendrimers revealed their violet and blue fluorescent properties, thus, promoting them as promising materials for emission 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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The platinum(0)-diphosphine complex [Pt(CO)(L1)] (3, where L1 = 1,2-C6H4(CH2PtBu2)2) and its diphosphinite analogue [Pt(CO)(L2)] (11, where L2 = 1,2-C6H4(OPtBu2)2) act as Lewis bases in conjunction with the main group Lewis acid B(C6F5)3 to form frustrated or cooperative Lewis pairs. These systems activate dihydrogen, ethene/carbon monoxide, and phenylacetylene, leading to products that depend on the exact ligand used. These subtle changes to ligand structure influence reactivity, most notably in hydrogen activation where a variety of dinuclear species of the type [(diphos)Pt(mu-H)3Pt(diphos)]+ or [(diphos)Pt(mu-H)(mu-CO)Pt(diphos)]+ are observed. Activation of ethene with the Lewis pair leads to a previously reported coupling product and the mechanism is probed. The basicity of [Pt(CO)(L)] is demonstrated by deprotonation of phenylacetylene. Preliminary studies with an analogous palladium complex [Pd(CO)(L1)] 33 suggests related chemistry may be exploited for this metal. These results provide further examples of cooperative Lewis pair behavior in which one of the components is based on a transition metal complex.

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