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The Pd-catalyzed 3-arylation of 2-oxindoles with aryl bromides, chlorides and triflates is found to proceed using i -Pr-BI-DIME and Me 2 -BI-DIME ligands. The mono-arylation of 3-unsubstituted oxindoles is accomplished using a Pd 2 (dba) 3 / i -Pr-BI-DIME catalyst system, and gives good yields of 3-aryloxindoles from aryl bromides and chlorides. The arylation of 3-substituted oxindoles is also possible using this catalyst/ligand system. The asymmetric arylation of 3-substituted oxindoles is accomplished using Me 2 -BI-DIME to furnish oxindoles bearing a quaternary C-3 stereocenter in enantiomeric ratios of up to 93:7.

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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 efficient and practical protocol for the synthesis of (E)-allylethers from readily available olefins with alcohols or phenols was developed. This aerobic oxidative allylic C-H oxygenation protocol features mild conditions, broad substrate scope, and high atom and step economy, making it a valuable and convenient synthetic method. Notably, molecular oxygen is the sole oxidant in this novel transformation.

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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 palladium(0)-catalyzed, ligand-controlled, regioselective addition of diaryl acetonitrile pronucleophiles to propargylic carbonates is reported. Selective formation of either terminal 1,3-dienyl or propargylated products is proposed to arise from a change in reaction mechanism controlled by the denticity of the coordinating ligand.

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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 present invention relates to chemical compounds having a general formula I wherein A1-8, D?, L1, L2, R1, R6-8 and n are defined herein, and synthetic intermediates, which are capable of modulating various protein kinase receptor enzymes and, thereby, influencing various disease states and conditions related to the activities of such kinases. For example, the compounds are capable of modulating Aurora kinase thereby influencing the process of cell cycle and cell proliferation to treat cancer and cancer-related diseases. The invention also includes pharmaceutical compositions, including the compounds, and methods of treating disease states related to the activity of Aurora kinase.

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

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Water-soluble diol-functionalized imidazolium ionic liquid 1, prepared from 2,2-bis(1-methyl-methyl-imidazolium)propane-1,3-diol bromide, potassium hydroxide, and malononitrile, was used as an efficient phosphine-free ligand for palladium-catalyzed arylation of aryl halides with acrylates in aqueous phase under mild conditions. It was found that the synergistic coordinating action of diol-functionalized imidazolium cation with CN-containing anion played the key role in improving the activity and stability of the catalyst. Water-soluble diol-functionalized imidazolium ionic liquid 1, prepared from 2,2-bis(1-methyl-methylimidazolium)propane-1,3-diol bromide, potassium hydroxide, and malononitrile, was used as an efficient phosphine-free ligand for palladium-catalyzed arylation of aryl halides with acrylates in aqueous phase under mild conditions. 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 novel, selective palladium-catalysed carbenoid C(aryl)-H insertion of alpha-diazo-alpha-(methoxycarbonyl)acetanilides leading to oxindoles is 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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The mechanism of the palladium-catalyzed synthesis of allylic silanes and boronates from allylic alcohols was investigated. 1H, 29Si, 19F, and 11B NMR spectroscopy was used to reveal key intermediates and byproducts of the silylation reaction. The tetrafluoroborate counterion of the palladium catalyst is proposed to play an important role in both catalyst activation as well as the transmetalation step. We propose that BF3 is generated in both processes and is responsible for the activation of the substrate hydroxyl group. An (eta3- allyl)palladium complex has been identified as the catalyst resting state, and the formation of (eta3-allyl)palladium complexes directly from allylic alcohols has been studied. Kinetic analysis provides evidence that the turnover limiting step is the transmetalation, and insights into notable similarities between the borylation and the silylation reaction mechanisms enabled us to considerably improve the stereoselectivity of the borylation.

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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 the synthesis and characterization of a series of p-type copolymers, which combine a fluorinated quinoxaline (FQ) acceptor unit either with a differently substituted benzodithiophene (BDT) or an unsubstituted thieno[3,2-b]thiophene (TT). The effect of the structural modifications on the photochemical stability of the resulting films is investigated and then correlated with the photovoltaic performance and lifetime measurements of corresponding photovolatic devices. To this end, we firstly studied the intrinsic stability of each polymer film by monitoring the UV-vis absorption decay, under simulated sunlight, as a function of ageing time. Bulk heterojunction solar cells, based on these polymers as donor materials, were fabricated and tested. Beside the initial values, we monitored the photovoltaic performance during prolonged light soaking in order to evaluate and compare the photostability of more complex systems such as working solar cells.

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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 unique properties conferred by the incorporation of fluorine into organic molecules has resulted in the widespread use of organofluorine compounds in the pharmaceutical and agrochemical industries. In contrast, organofluorine compounds are exceedingly rare in nature. The dearth of chiral pool organofluorine compounds necessitates the development of stereoselective methods for the incorporation of carbon?fluorine bonds into organic molecules. A wide variety of catalytic, enantioselective fluorination methods have been developed to address this challenge, including Lewis acid catalysis, organocatalysis, transition metal catalysis, and phase transfer catalysis. Using these methods, carbonyl compounds, alkenes, allylic electrophiles, aziridines, and epoxides have been engaged in catalytic, enantioselective fluorination reactions. This chapter provides a comprehensive review of the methods available for the catalytic, enantioselective construction of carbon?fluorine bonds and is subdivided into electrophilic and nucleophilic fluorination reactions. The chapter also provides a comparison with diastereoselective transformations and enantioselective functionalization reactions of fluorinated substrates.

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

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Metal-coordinating directing groups have seen extensive use in the field of transition-metal-catalyzed alkene functionalization; however, their waste-generating installation and removal steps limit the efficiency and practicality of reactions that rely on their use. Inspired by developments in asymmetric organocatalysis, where reactions rely on reversible covalent interactions between an organic substrate and a chiral mediator, we have developed a transient-directing-group approach to reductive Heck hydroarylation of alkenyl benzaldehyde substrates that proceeds under mild conditions. Highly stereoselective migratory insertion is facilitated by in situ formation of an imine from catalytic amounts of a commercially available amino acid additive. Computational studies reveal an unusual mode of enantioinduction by the remote chiral center in the transient directing group.

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