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1,3-Diazetidinones are obtained by bis(dibenzylideneacetone) palladium(O)-catalyzed carbonylation of diaziridines having one substituent attached to the ring carbon atom. This regiospecific insertion into the nitrogen-nitrogen bond also occurs for 3,3-disubstituted diaziridines, provided one uses stoichiometric quantities of cobalt carbonyl.

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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 cyclization of benzamide derivatives that contain an alkyne by a Pd(0)/dialkyl(biaryl)phosphine catalytic system is reported. The reaction efficiently provides a variety of six-membered N-heterocyclic compounds that contain a fully substituted carbon center without the need for a stoichiometric additive. Mechanistic studies suggest that this unprecedented cyclization starts with the cleavage of a propargylic C-O bond, and a 1,3-diene has been identified as a relevant intermediate.

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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 kinetics of the oxidative addition of bidentate ligand-chelated Pd 0 complexes to phenyl iodide and bromide has been studied via cyclic voltammetry. The dibenzylideneacetone (dba) delivered by the palladium precursor Pd(dba)2 was found to affect the concentration of the more reactive dba-free Pd0 complex and consequently the kinetics of the overall oxidative addition. The complexes generated from Pd(dba)2 and PhSCH2CH2SPh (pte) were found to be considerably more reactive than those generated from Pd(dba)2 and Ph 2PCH2CH2-PPh2 (dppe). The former complexes can react with PhBr at low temperatures.

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

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Provided are asymmetric arylamine derivatives for an organic electroluminescent element, represented by the formula (1), which is prepared by sequentially inducing a secondary amine and a tertiary amine to an aryl compound Ar core so that they do not include a symmetrical axis and a symmetrical surface in a molecule, a manufacturing method of the same, an organic thin layer material including the asymmetric arylamine derivatives, and an organic electroluminescent element employing the same: wherein Ar represents a C10-C20 divalent aryl group, Ar1 is a divalent C6-C30 aryl group, and Ar2 to Ar5 each independently represents a divalent C6-C30 aryl group, at least one of Ar2 to Ar5 having a different structure when the secondary amine and the tertiary amine in Ar are substituted at symmetrical positions, and Ar2 to Ar5 having the same structure or different structures when the secondary amine and the tertiary amine in Ar are substituted at asymmetrical positions. The asymmetric arylamine derivative can be used in forming an organic thin layer for an organic electroluminescent element. When the organic electroluminescent element is formed using a dopant as an emitting material, the asymmetric arylamine derivative exhibits superb emission efficiency and an excellent lifetime characteristic in a blue wavelength region.

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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 traceless protecting strategy is presented for the long-standing challenge of conducting the palladium-catalyzed alpha-arylation of carboxylic aids and secondary amides with aryl halides. Both of the presented coupling processes occur with a variety of carboxylic acids and amides and with a variety of aryl bromides containing a broad range of functional groups, including base-sensitive functionality like acyl, alkoxycarbonyl, nitro, cyano, and even hydroxyl groups. Five commercial drugs were prepared through this method in one step in 81-96% yield. Gram-scale synthesis of medication Naproxen and Flurbiprofen with low palladium loading further highlights the practical value of this method.

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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 synthesis of a palladium complex and a monosilylated monomer derived from 15-membered azatriolefinic macrocycle are described as well as the preparation of the corresponding hybrid organic-inorganic materials, containing a macrocyclic palladium(0) complex covalently anchored to the silica matrix. The materials were obtained by sol-gel process using different routes: post-synthesis treatment on a mesostructured silica, cogelification of a monosilylated precursor and tetraethylorthosilicate. The activity of the different materials as recoverable catalysts in Suzuki cross-couplings is reported and commented.

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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-catalyzed asymmetric side-chain C(alpha)-allylation of 2-alkylpyridines, without using an external base, was developed. The high linear selectivities and enantioselectivities were achieved using new chiral diamidophosphite monodentate ligands. Given that the reaction conditions do not require an external base, this catalyst system enabled chemoselective C(alpha)-allylation of 2-alkylpyridines containing alpha-carbonyl C?H bonds, which are more acidic than alpha-pyridyl C?H bonds.

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

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Thiazole-containing pi-conjugated moieties are important structural units in the development of new electronic and photochromic materials. We have developed a Pd-catalyzed syn-hydroarylation reaction of diaryl alkynes with thiazoles that provides access to thiazole-containing triarylethylenes. Pd(II) complexes derived from Pd(0) species and carboxylic acids facilitated C-H functionalization of the unsubstituted thiazole with high C5 selectivity. The catalytic system was also compatible with other azoles, such as oxazoles and a pyrazole, allowing the stereoselective syntheses of various trisubstituted olefins.

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

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Several new neutral and cationic organopalladium complexes containing a P-N chelating ligand, 2-(diisopropylphosphinomethyl)-1-methylimidazole, have been synthesized and characterized. The neutral complexes [PdPh(I)(P-N)] 1 and [PdMe(I)(P-N)] 2 have been synthesized by oxidative addition of PhI and MeI, respectively to Pd(dba)2 (dba = dibenzylideneacetone) in the presence of the P-N ligand. The cationic complexes [PdPh(PPh3)(P-N)]BF4 3 and [PdMe(PPh3)(P-N)]BF4 4 were obtained by adding an acetone solution of AgBF4/PPh3 to the corresponding neutral precursors 1 and 2, respectively. A cationic allyl complex, [Pd(eta3-C3H5)(P-N)]Br 5, has also been prepared by oxidative addition of 3-bromopropene to Pd(dba)2 in presence of the P-N ligand. Single crystal structure determinations have been carried out for 1, 4 and 5. Carbonylation of the metal-carbon bond in these new complexes was also studied. The neutral complexes 1 and 2 react smoothly with CO to give carbonylated products [Pd(C(O)Ph)I(P-N)] 6 and [Pd(C(O)Me)I(P-N)] 7, respectively. The methyl complex 2 reacted much faster than the phenyl complex 1. The cationic complexes 3 and 4 are inert and do not give any carbonylated product. However, in the case of the reaction of 3, evidence has been obtained for the formation of a CO-coordinated complex [PdPh(PPh3)(CO)(P-N)]BF4 8 in which the P-N ligand temporarily acts as a monodentate phosphorus-bonded ligand. On the other hand, a cationic complex containing a weakly coordinating acetone molecule, [PdMe{(CD3)2CO}(P-N)]BF4 9, showed an enhanced reactivity toward CO and gave [Pd{MeC(O)}(CO)(P-N)]BF4 10.

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

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Four three-coordinate arylpalladium amido complexes with a single hindered phosphine were isolated and structurally characterized. Each possessed a T-shaped geometry. Several of these complexes possessed true three-coordinate structures that lacked any additional coordination by ligand C-H bonds. All of the three-coordinate complexes underwent reductive elimination to form the corresponding triarylamine. A comparison of the rate of reaction of the three-coordinate compounds demonstrated that the rate of elimination from the pentaphenylferrocenyl di-tert-butylphosphine complex were the fastest. A comparison of the rates of reactions between three-coordinate and four-coordinate complexes showed that the rates were much faster from the three-coordinate complexes. Copyright

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