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We report the synthesis and reactivity of 4-fluorosydnones, a unique class of mesoionic dipoles displaying exquisite reactivity towards both copper-catalyzed and strain-promoted cycloaddition reactions with alkynes. Synthetic access to these new mesoionic compounds was granted by electrophilic fluorination of sigma-sydnone PdIIprecursors in the presence of Selectfluor. Their reactions with terminal and cyclic alkynes were found to proceed very rapidly and selectively, affording 5-fluoro-1,4-pyrazoles with bimolecular rate constants up to 104m?1s?1, surpassing those documented in the literature with cycloalkynes. Kinetic studies were carried out to unravel the mechanism of the reaction, and the value of 4-fluorosydnones was further highlighted by successful radiolabeling with [18F]Selectfluor.

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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 catalytic alpha-arylation of indolin-3-ones was developed. The catalytic system comprising Pd(dba)2 and PAd3 was found to be optimal for the transformation. The protocol features broad functional group compatibility in that a range of arylated indoxyl derivatives bearing a fully substituted carbon center was synthesized with high efficiency. A preliminary bioassay study revealed that the selected indole-substituted indolin-3-ones exhibit favorable cytotoxic activities against HCT-116 cancer cell line.

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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 rate of palladium catalysed phenylation of allylic alcohols is markedly enhanced by addition of tertiary amines, presumably by co-ordination to the palladium atom to form very reactive species.

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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 in-depth mechanistic study on the palladium-catalyzed direct arylation of imidazoles at the C-5 position is presented. The interactions of triphenylphosphine (PPh3)-ligated aryl-Pd species with 1,2-dimethyl-1H-imidazole (dmim) have been studied in detail. In contrast with previous suggestions, phosphine-ligated organo-Pd species are not active and the reaction proceeds through imidazole-ligated organo-Pd intermediates. The kinetics of the oxidative addition of aryl halides with dmim-ligated Pd(0) species have been characterized in a Pd(dba)2/dmim model system. A thorough study of the equilibria involving novel [ArPd(dmim)2X] complexes (X=I, OAc) and the unexpected cationic [ArPd(dmim)3]+ is also reported. The ability of these species to effect the C-H arylation of dmim at room temperature in the presence of acetate is also demonstrated.

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

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Functionalised cyclic enol ethers can be recovered with high levels of enantiocontrol after an asymmetric catalytic [1,3]-rearrangement reaction. These compounds can be further elaborated to a series of carbo- and heterocyclic products in good yield and with excellent levels of stereocontrol.

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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 lactonization of unactivated aryl C-H bonds with CO2 to afford important phthalides is reported. Notably, this method features high selectivity, excellent functional group tolerance, smooth scalability, and facile product diversification. DFT calculations reveal that a novel insertion of two CO2 into the O-Pd bond of a palladacycle might be the key step, providing great potential and a different perspective for carbonylation with CO2.

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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 convenient and regioselective synthesis of two series of indolo[2,3-b]quinolines, namely 10H-indolo[3,2-b]quinolines and 6H-indolo[2,3-b]quinolines, has been developed. The synthesis, proceeds in moderate to high yields, involving chemoselective palladium catalyzed Suzuki reaction of 2,3-dihaloquinolines with 2-bromophenylboronic acid, followed by a double Buchwald-Hartwig C-N coupling.

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

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Macrobicycles comprising a central diazacrown structural unit were modified with two 3-bromobenzyl substituents and the resulting compounds were introduced in Pd(0)-catalyzed macrocyclization reactions with trioxadiamine, to give cryptand-like macrotricycles. In the second approach, diazacrown ethers were substituted with two 3,5-dibromobenzyl groups and their Pd(0)-catalyzed double macrocyclization with a series of oxadiamines produced a new family of trimacrocyclic compounds; the Pd(dba)2/RuPhos catalytic system was found to be the most efficient. The decoration of one trimacrocycle with four dansyl fluorophore groups produced a fluorescent molecular probe for Cu(II) and Al(III) cations.

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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 detailed mechanism study on the anion ligand promoted selective C-H bond fluorination is reported. The role of the anion ligand has been clarified by experimental evidence and DFT calculations. Moreover, the nitrate promoted C-F bond reductive elimination enabled a selective C-H bond fluorination of various symmetric and asymmetric azobenzenes to access diverse o-fluoroanilines.

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

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(E,E,E)-1,6,11-Tris(arenesulfonyl)-1,6,11-triazacyclopentadeca-3,8,13-trienes (1) form very stable complexes with Pd0 and Pt0, and moderately stable complexes with Ag1. The three olefins in the macrocycle are responsible for the complexation. The X-ray structures of two complexes of Pd0 and Pt0 are presented; both complexes are planar trigonal.

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