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Heck arylation of allyl alcohol catalyzed by Pd(0) nanoparticles

Pd(0) nanoparticles ca. 2 nm in diameter were obtained by the reduction of PdCl2 and Pd(OAc)2 in water at 80 C in the presence of a PVP-stabilizing polymer. Pd(0) NPs were successfully used in the Heck coupling of allyl alcohol with iodo- and bromobenzenes. Iodobenzenes reacted under solventless conditions or in DMF solution producing 3-arylpropanals and 2-arylpropanals as the main products. The same products were obtained in the reaction of bromobenzene in TBAB as the reaction medium. The stability of Pd(0) NPs was evidenced in recycling experiments. Similar Heck coupling results were also obtained with the palladium compounds PdCl2(cod) and Pd(OAc)2 under the same conditions.

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

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Ir-catalyzed borylation of C-H bonds in N-containing heterocycles: Regioselectivity in the synthesis of heteroaryl boronate esters

(Chemical Equation Presented) Blocking the way: Substitution at the 2-position in pyridines and other N-heterocycles blocks N-coordination to an Ir center. This steric hindrance provides a substrate-design criterion that allows the Ir-catalyzed borylation of C-H bonds, which can be followed by Suzuki-Miyaura cross-coupling in a one-pot reaction (see scheme; B 2pin2 = bis(pinacolato-O,O?)diboron, dtbpy = 4,4?-tBu2-2,2?-bipyridine).

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

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Interactions of cationic palladium(II)- and platinum(II)-eta3- allyl complexes with fluoride: Is asymmetric allylic fluorination a viable reaction?

The complex cations [M(eta3-R2All)(PPFPz{3-tBu})] + (M = PdII, R2All = 1,3-diphenylallyl, 1,3-dicyclohexylallyl, indenyl; M = PtII, R2All = 1,3-diphenylallyl; PPFPz-{3-tBu} = 3-tert-butyl-1-{1-[2-diphenylphosphanyl- ferrocenyl]ethyl}-1H-pyrazole) have been prepared as salts with PF 6- or SbF6-. They have been characterized by NMR spectroscopy in solution and by X-ray crystallography in the solid state. Their reactions with sources of nucleophilic and “naked” fluoride have been investigated by multinuclear NMR spectroscopy. The PdII complexes did not undergo any nucleophilic substitution with concomitant release of allyl fluorides. The dicyclohexylallyl fragment was released as a 1,3-diene by elimination, but with other allyl complexes nonspecific decomposition reactions predominated. The complex [Pt(eta3-1,3-Ph2C3H3)-(PPFPz{3- tBu})]PF6 underwent an anion exchange with Me4NF to give [Pt(1,3-Ph2C3H3)(PPFPz{3-tBu})]F which existed as a mixture of interconverting allyl isomers in solution at ambient temperature. For the bromide salt, [Pt(eta3-1,3-Ph 2C3H3)(PPFPz{3-tBu})]Br, allyl isomerization was slow at ambient temperature. Precursors of Pt0 reacted with bromo-1,3-diphenylprop-2-ene to give [Pt2(mu-Br) 2(eta3-1,3-Ph2All)2] and precursors of Pd0 underwent oxidative additions with bromo- and fluoro-1,3-diphenyl-2-propene to give 1,3-diphenylallyl complexes of Pd II. Therefore, the nucleophilic attack of fluoride on the allyl fragment of PdII complexes is endergonic, and the high energy barrier of this step is difficult to overcome in a catalytic allylic fluorination reaction. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.

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

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A Convenient Synthesis of (E)-beta-Ethoxycarbonylvinylsilanes by Palladium-catalysed Regio- and Stereo-specific Hydroesterification of Trimethylsilylacetylenes

Palladium-catalysed hydroesterification of trimethylsilylacetylenes 1 gives (E)-beta-ethoxycarbonylvinylsilanes 2 exclusively in excellent yields.

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

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Spin-Transition Behaviour of Transition Metal Complexes with 2,6-bis-(Benzimidazol-2′-yl)-pyridine Induced by Deprotonation of the Complex

2,6-bis-(Benzimidazol-2′-yl)-pyridine (bzimpy = H2L) acts as a bidentate ligand when combining with transition metal ions.The complexes (ClO4)2 (M = Fe(2+), Mn(2+), Zn(2+), Co(2+), and Ni(2+)) were obtained as solids.The protonation constants (log K) for the ligand and the complexes were evaluated in 30:70 (v/v) H2O:EtOH at 293 K and at constant ionic strength of 0.12M KCl.Coordination of the ligand to the metal ions leads to an increase of acidity of the imino-hydrogen of the benzimidazole group of the ligand as a function of the complex stability.Deprotonation leads to a spin-state transition (intermediate spin-state –> low-spin) of the iron(II)-complex, followed by a shift of the metal-to-ligand charge transfer band (MLCT) to lower energies (lambdamax = 563 to 580 nm).The d-d absorption bands are found to shift to higher energies and the low-spin isomer is favoured at room temperature.An opposite shift of the MLCT band (lambdamax = 563 to 557 nm) is observed when HClO4 is added to the complex solution, rendering the high-spin state of the complex more favourable. – Keywords. 2,6-bis-(Benzimidazol-2′-yl)-pyridine; Spin-Crossover behaviour; Deprotonation; Transition metal complexes.

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

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Convenient synthetic route to palladium complexes of unconventional N-heterocyclic carbenes derived from pyridazine and phthalazine

Several Pd(II) complexes with unconventional pyridazine- and phthalazine-derived carbene ligands were synthesized via direct oxidative addition of Cl derivatives of the alkylated diazine heterocycles to Pd(0) species. The alkylated ligand precursors are readily prepared from commercial starting materials, and oxidative addition is regioselective. DFT calculations confirm that the thermodynamically favored products are formed. Four complexes (1-4) have been fully characterized, including by X-ray crystallography. Attractive intramolecular pi-pi stacking between the electron-poor N-alkylated diazine heterocycles and adjacent phenyl groups of the PPh 3 coligands is revealed by the solid-state structures.

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

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Oxidative Mechanochemistry: Direct, Room-Temperature, Solvent-Free Conversion of Palladium and Gold Metals into Soluble Salts and Coordination Complexes

Noble metals are valued, critical elements whose chemical activation or recycling is challenging, and traditionally requires high temperatures, strong acids or bases, or aggressive complexation agents. By using elementary palladium and gold, demonstrated here is the use of mechanochemistry for noble-metal activation and recycling by mild, clean, solvent-free, and room-temperature chemistry. The process leads to direct, efficient, one-pot conversion of the metals, including spent catalysts, into either simple water-soluble salts or metal?organic catalysts.

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

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4-ALKYL SUBSTITUTED 3,4-DIHYDROPYRROLO[1,2-a]PYRAZIN-1(2H)-ONE DERIVATIVES AS KINASES INHIBITORS

The present invention relates to 4-alkyl substituted 3,4-dihydropyrrolo[1,2-a]pyrazin-1(2H)-one derivatives which modulate the activity of protein kinases and are therefore useful in treating diseases caused by dysregulated protein kinase activity. The present invention also provides methods for preparing these compounds, pharmaceutical compositions comprising these compounds, and methods of treating diseases utilizing such these compounds or the pharmaceutical compositions containing them.

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

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Effect of heterocycles on field-effect transistor performances of donor-acceptor-donor type small molecules

Two D?A?D small molecules comprising triphenylamine and diketopyrrolopyrrole were synthesized having either furan or thiophene connected to the fused lactam ring. In this design, furan/thiophene diketopyrrolopyrrole acts as an acceptor and triphenylamine acts as a donor. Propeller shaped triphenylamine has its effect on packing, processability and plays a vital role in determining the pi-pi molecular orbital stacking in such compounds and thus the mobility of charge carriers. With TDPPT and FDPPT, maximum hole carrier mobility obtained is 2.88?¡Á?10?3?cm2?V?1?s?1and 1.60?¡Á?10?3?cm2?V?1?s?1, respectively using bottom gate bottom contact field-effect transistor.

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

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Vasculostatic agents and methods of use thereof

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