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Silver carboxylate salts are widely used as additives in palladium-catalyzed C-H functionalization reactions. However, the role of these silver additives is often not fully understood. This paper describes an investigation of the role of AgOPiv in the stoichiometric activation of C6F5H at a well-defined PdII complex as well as in the PdII-catalyzed oxidative dimerization of 2-alkylthiophenes. Both in situ NMR spectroscopy and H/D exchange studies of the reactions of C6F5H implicate a role for AgOPiv in the C-H cleavage event, generating Ag-C6F5 as an intermediate. The catalytic studies show similar trends despite the different conditions and substrates, suggesting that AgOPiv promotes a similar metalation of the thiophene in the catalytic transformations. This proposal is supported by DFT calculations, which show energetically feasible pathways for concerted metalation-deprotonation of both 2-methylthiophene and pentafluorobenzene at [Ag(OPiv)]2. These studies suggest that initial metalation of C-H substrates at AgI carboxylates should be considered as a plausible pathway in C-H functionalization reactions involving mixtures of Ag and Pd salts.

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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 heterocycle-containing diarylmethane synthesis from chloromethyl(hetero)arenes with (hetero)arylboron reagents was attained using the palladium/ether-imidazolium chloride system. This coupling process tolerated a diverse range of heteroaromatic moieties with sufficient catalytic activity to achieve the efficient synthesis of various diheteroarylmethanes in good to excellent yields.

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

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This account deals with the chemical functionalizations of polystyrene and polystyrene-containing materials and the related applications. The functionalizations herein tackled concern those reported from the turn of the last century up to now. As per the coveted applications, either conventional or modern chemistries, such as click reaction are applied to chemically modify polystyrene. Besides the classical polymerization methods for the synthesis of polystyrene and polystyrene-containing materials, the newly emerged techniques, such as living controlled radical polymerization, are duly evoked. Both soluble and insoluble polystyrene resins were subjected to bulk or surface functionalizations. Surface treatments with plasma, laser, or UV beam in the presence of oxygenated or aminated chemicals led to hydrophilic surface-functionalized polystyrenes. Applications of functionalized polystyrenes herein discussed include organic synthesis, polymer synthesis, separation and adsorption of metals and biomolecules, biological activity, light emission/absorption, electroactivity, and nanoparticles design.

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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 method for the synthesis of 4-substituted azabicyclo[3.2.1]octanes from N -tosyl-2-azabicyclo[3.2.1]octa-3,6-diene, a versatile bicyclic heterocycle not commonly used in medicinal chemistry research, is presented. The method uses bromination, followed by Suzuki coupling, and subsequent reduction and deprotection. The desired 4-substituted azabicyclo[3.2.1]octanes were obtained in moderate to high yields.

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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 Formula (I) along with processes for their preparation that are useful for treating, managing and/or lessening the diseases, disorders, syndromes or conditions associated with the modulation of calcium sensing (CaSR) receptors. Methods of treating, managing and/or lessening the diseases, disorders, syndromes or conditions associated with the modulation of calcium sensing (CaSR) receptors of Formula (I).

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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 first catalytic enantioselective total synthesis of (-)-podophyllotoxin is accomplished by a challenging organocatalytic cross-aldol Heck cyclization and distal stereocontrolled transfer hydrogenation in five steps from three aldehydes. Reversal of selectivity in hydrogenation led to the syntheses of other stereoisomers from the common precursor.

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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 process for synthesizing 7-alkynyl-4-aminoquinazolines from 7-haloquinazolines is disclosed. In one specific synthesis, 4-[N-3-chloro-4-fluorophenyl)]-7- [3-methyl-3-(4-methyl-l-piperazinyl)-l- butynyl]-6-[N-inethyl acrylamide] quinazoline is prepared from 7-chloro-6-nitro-3H-quinazolin-4-one. Also disclosed is an intermediate useful in the syntheses of 7-alkynyl-4-ammoquinaozolines and a process for making the intermediate. The 7-alkynyl-4-aminoquinaozolines prepared by processes of the invention are useful as pharmaceutically active compounds.

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

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n-Type conjugated polymers were synthesized by using pyromellitic diimide monomers with two different alkyl side chain substitutions as electron-accepting units and benzodithiophene as electron-donating unit via Stille coupling reaction. The obtained polymers were characterized by UV-vis spectroscopy and cyclic voltammetry. The results illustrate that the substituted alkyl side chains 2-ethylhexyl and 2-octyldodecyl have negligible effect on the optical properties of the resulting polymers. The LUMO levels of the polymers located at -3.5 to -3.6 eV. All-polymer bulk heterojunction solar cell with “P3HT” as p-type polymer in standard architecture were fabricated, the cell based on the polymer with 2-octyldodecyl side chain (P2) shows good photovoltaic performance with power conversion efficiency up to 0.47% and a high open circuit voltage of 0.96 V.

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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 series of 8-amino imidazo[1,2-a]pyrazine derivatives has been developed as inhibitors of the VirB11 ATPase HP0525, a key component of the bacterial type IV secretion system. A flexible synthetic route to both 2- and 3-aryl substituted regioisomers has been developed. The resulting series of imidazo[1,2-a]pyrazines has been used to probe the structure-activity relationships of these inhibitors, which show potential as antibacterial agents.

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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 environmentally benign microwave-assisted domino [Pd]-catalyzed reaction, for the efficient and diverse synthesis of 3,3?-disubstituted indolines, oxindoles, and dihydrobenzofurans, is presented. Significantly, water served as the sole green solvent and the strategy displayed an excellent functional-group tolerance. Remarkably, the process was also amenable to unmasked functional groups and furnished the products, in very good to almost quantitative yields.

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