Palladium! II chloride, bis

Acetylenes, tri- and tetramerization Bis-(benzonitrile>palladium (II) chloride. Bis-triphenylphosphinecarbonylmckel. Tetrakis-phosphorus trichloride-nickel (0). Titanium tetrachloride. 

Palladium(II) chloride, bis(triphenylphosphine) complex-copper(I) iodide. 

Bis(benzonitrile)palladium(II) chloride, benzene, reflux, 16-20 h, 86% yield. 

In the presence of triphenylphosphine and four equivalents of chloride, (1-butyl-3-methylimida2olylidene)bis(triphenylphosphine)palladium(II) chloride is formed (Scheme 6.1-4). 

Palladiumphthalocyanine (PcPd) can be synthesized from phthalimide, ammonium molyb-date(VI), urea and palladium(II) chloride in nitrobenzene.285 Peripherally substituted palladium phthalocyanine is prepared by the reaction of phthalonitrile286 or isoindolinediimine114,117 and palladium(II) acetate in 2-(dimethylamino)ethanol. Also a metal insertion into metal-free phthalocyanine in dimethylfonnamide starting from bis(triphenylphos-phane)palladium(II) chloride has been performed.141,287... 

In the ligand l,2-bis-(2-pyridylethynyl)benzene the pyridyl N atoms easily attain the appropriate separation for trans-chelation of metal cations. The 1 1 complex of the ligand with palladium(II) chloride has been structurally characterized.171,182... 

Palladium (II) chloride and ferric (III) chloride were purchased from Sigma Chemicals Co. Cerium(III) nitrate from Pfaltz Bauer, Inc. y-Al203 (100 m2/g) from Alfa Chemicals ethanol (HPLC grade) and nitrobenzene (Certified ACS) from Fisher Scientific. Bis(triphenylphosphine)palladium(II) dichloride was generously donated by Dr. Ivan J.B. Lin (National Dong Hwa University, Taiwan). All compounds were used without further treatment. Carbon monoxide (99.0%) was obtained from Praxair. 

Only one report mentions the cyclopropanation with diazodiphenylmethane in the presence of a group VIII metal catalyst. Remarkably enough, the selectivity of the reaction with 5-methylene-bicyclo[2.2.1]hept-2-ene (8) can be reversed completely. With Rh2(OAc)4 as catalyst, the exocyclie double bond is cyclopropanated exclusively (>100 1), whereas in the presence of bis(benzonitrile) palladium(II) chloride the endocyclic C=C bond is attacked with very high selectivity (>50 1)47). 

The palladium nanoparticle is prepared from the reaction of the stabilizer, 4,4 -bis(perfluorooctyl)dibenzylideneacetone with palladium(II) chloride. The average size of the nanoparticle varied according the ratio of PdCF to the stabilizer, but was typically around 4 or 5 nm. The initial yield observed in the Suzuki coupling reaction was 90%, but decreased to 78% after five consecutive runs. Fluorous boronates (alternative precursors in Suzuki reactions), have also been developed for use in fluorous biphasic processes [12], A generic structure of a fluorous boronate is shown in Figure 10.2. 

Methyl 5-fluoro-4-(trifluoromethylsulfonyloxy)-2,3-dihydro-l-methyl-7-0X0-1//,7//-pyrido[3,2,l-iy]cinnoline-8-carboxylate(68,R = Me,R = R = H, R = F, R = Me, R = CF3SO2O) was reacted with 3-tributylstannyl-2-cyclohexen-l-one in the presence of lithium chloride and bis(triphenyl-phosphine)palladium(II) chloride in tetrahydrofuran for 3 days to give a 4-(3-oxo-l-cyclohexen-l-yl)derivative (92EUP470578). 

Palladium appears to be especially suitable for forming these complexes. As an example, allyl alcohol reacts with palladium (II) chloride (236) to give bis(allylpalladium chloride), [(C3H6)PdCl]2. Its nmr spectrum shows three peaks (56), in the ratio 1 2 2, indicating the structure shown in Fig. 20. The exact location of the allyl groups with respect to the metal... 

In a 5 mL round-bottomed flask equipped with a magnetic stirrer was placed bis(benzonitrile)palladium(II) chloride under nitrogen. To this flask was added (R)-2-[2-(diphenylphosphanyl)phenyl]-7-isopropyl-6,7-dihydro-5H-l-pyrindine (2.3 mg) in anhydrous THF (0.4 mL) and the mixture was stirred at room temperature for 1 h. 

Bis(acetylacetonate)zinc(II), 33 Carbon monoxide, 66 of nitrogen compounds Palladium(II) chloride-Copper(II) chloride, 235... 

Osmium tetroxide-N-Methyl-morpholine N-oxide, 222 Osmium tetroxide-Trimethylamine N-oxide-Pyridine, 223 Palladium Compounds Benzylchlorobis(triphenylphosphine)-palladium(II), 30 Bis (ace tonitrile) chloronitropalla-dium(II)-Copper(II) chloride, 33 Bis(acetonitrile)dichloropalladium(II), 33, 211, 236... 

Palladium(II) chloride (Johnson Matthey) and 10% Pd/C (Aldrich) were used as received. Bis[(methallyl)chloropalladium(II)] (ref. 8), bis(dibenzylideneacetone)palladium(0) (ref. 9), metho-xyoctadienes (ref. 10), l-methoxy-3-octene (ref. 11), methoxyallyle and cis + traru-methoxycrotyle (ref. 12) were prepared as described in the literature. 

The rhodium(II) catalysts and the chelated copper catalysts are considered to coordinate only to the carbenoid, while copper triflate and tetrafluoioborate coordinate to both the carbenoid and alkene and thus enhance cyclopropanation reactions through a template effect.14 Palladium-based catalysts, such as palladium(II) acetate and bis(benzonitrile)palladium(II) chloride,l6e are also believed to be able to coordinate with the alkene. Some chiral complexes based on cobalt have also been developed,21 but these have not been extensively used. 

Dich lorotris(triphenylphosphine)-ruthenium. Dimethyl(2,4,6-tri-/-butylphenoxy)chlorosilane. Lithiocyclopropyl phenyl sulfide. Nafion-H. PaLIadium(II) acetate-1,2-Bis(diphenylphosphino)ethane. Palladium(II) chloride. Phenyltrimethylammonium perbromide. Potassium hydride. Potassium permanganate. 2-Pyridylsclcnenyl bromide. 

Palladium(ll) acetate, 389-392 Palladium(II) acetate-1,2-bis(diphenylphosphino)ethane, 391-392 Palladium acetate-triphenylphosphine, 392 Palladium catalysts, 392-393 Palladium(II) chloride, 393-394 Palladium(II) ehloride-eopper(I) cloride, 346 Palladium(II) chloride-silver(I) acetate, 396-397... 

Bis(phenylseleno)propene. Dichlorotris(triphenylphosphinc)-ruthcnium(ll). Palladium(II) chloride. 

Oxo-4//-pyrido[l,2-a]pyrimidine-7-carboxylates 500 were obtained when 7-iodo-4T/-pyrido[ 1,2-a]pyrimidines 499 reacted with carbon monoxide in the presence of bis(triphenylphosphine)palladium(II) chloride catalyst and triethylamine (Scheme 29) (94MI2). From 7-iodo derivatives 499, 7-vinyl derivatives 501 and 7-(l-ethoxyvinyl) derivatives 502 were prepared with vinyltributyltin in the presence of Pd(PPh3)4 and with (1-ethoxy-vinyl)tributyltin in the presence of bis(triphenylphosphine)palladium(II) chloride catalyst, respectively, in toluene at 80°C. 7-(l-Ethoxy vinyl)pyr-ido[l, 2-a]pyrimidin-4-ones 502 were hydrolyzed to yield 7-acetyl derivatives 503. The acetyl group of compounds 503 was reduced with sodium borohydride in the presence of cerium(III) chloride in ethanol to give 7-(1 -hydroxyethyl)pyridopyrimidin-4-ones 504. 

Diethyl(3-pyridyl)borane (3.38 g, 23 mmol) from Aldrich Chemical Co. Ltd. was added to a stirred solution of 3p-acetoxyandrosta-5,16-dien-17-yl trifluoromethanesulphonate (6.94 g, 15 mmol) in THF (75 ml) containing bis(triphenylphosphine)palladium(II) chloride (0.105 g, 0.15 mmol). An aqueous solution of sodium carbonate (2 M, 30 ml) was then added and the mixture heated, with stirring, by an oil bath at 80°C for 1 h, and allowed to cool. The mixture was partitioned between diethyl ether and water, the ether phase was dried (Na2C03), filtered through a short plug of silica, and concentrated. Chromatography, on elution with light petroleum-diethyl ether (2 1), afforded the 3 5-acetoxy-17-(3-pyridyl)androsta-5,16-diene (4.95 g, 84%) which crystallised from hexane, m.p. 144-145°C. 

To a solution of 2-iodo-5-(4-fluorophenylmethyl)thiophene (5.30 g, 16.6 mmol), in anhydrous DMF (5.0 ml) was added (R)-N-hydroxy-N-(3-butyn-2-yl)urea (2.12 g, 16.6 mmol), triphenylphosphine (84.0 mg, 0.32 mmol), bis(acetonitrile)palladium(II) chloride (40.0 mg, 0.16 mmol), copper(I) iodide (16.0 mg, 0.08 mmol), and diethylamine (5.6 ml). The mixture was stirred under nitrogen at room temperature for 22 h and concentrated in vacuum at 32°C. The residue was subjected to chromatography on silica eluting with 2-7% MeOH in CH2CI2, crystallization from ethyl acetate-hexane and trituration in CH2CI2 to afford (R)-N- 3-[5-(4-fluorophenylmethyl)thien-2-yl]-l-methyl-2-propynylVN-hydroxyurea as a cream-colored solid 0.94 g (18%), melting point 135°-136°C, (dec). 

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