Palladium compounds synthesis

Palladium Compounds, Complexes, and Ligands Widely Used in Organic Synthesis... 

J. Tsuji. Organic Synthesis with Palladium Compounds, Springer. Berlin. 1980. 

Other useful references are R. E. Heck, Palladium Reagents in Organic Synthesis Academic Press, New York, 1985, and J. Tsuji, Organic Synthesis with Palladium Compounds, Sptinger-Vedag, New York, 1980. 

The palladium compound [Pd(CNcy)2]3 has been made by metal vapour synthesis, from Pd atoms and a solution of cyNC at 160 K. It has an analogous structure [Pd3(CNcy)3( 2-CNcy)3] [60]. 

When the Pd bears chiral ligands, these reactions can be enantioselective. TT-Allylmolybdenum compounds behave similarly.Because palladium compounds are expensive, a catalytic synthesis, which uses much smaller amounts of the complex, was developed. That is, a substrate such as an allylic acetate, carbo-... 

Organomercurial carbonylation. Use of Co2(CO)g as a stoichiometric and as a catalytic reagent Organic synthesis reactions using palladium compounds Decarbonylation reactions using transition metal compounds... 

The copolymerization of carbon monoxide and a-olefins is one of the most challenging problems in polymer synthesis. Sen and his coworkers discovered that some cationic palladium compounds catalyze this alternative copolymerization, giving polyketones (Eq. 13). 

Palladium catalysts, 10 42 14 49 16 250 Palladium-catalyzed carbonylation, 13 656 Palladium chloride/copper chloride, supported catalyst, 5 329 Palladium compounds, 19 650-654 synthesis of, 19 652 uses for, 19 653-654 Palladium films, 19 654 Palladium membranes, 15 813 Palladium monoxide, 19 651 Palladium oxide, 19 601... 

When the Pd bears chiral ligands, these reactions can be enantioselective.1448 ir-Allylmo-lybdenum compounds behave similarly.1449 Because palladium compounds are expensive, a catalytic synthesis, which uses much smaller amounts of the complex, was developed. That is, a substrate such as an allylic acetate, alcohol, amine, or nitro compound1450 is treated with the nucleophile, and a catalytic amount of a palladium salt is added. The rr-allylpal-ladium complex is generated in situ. Alkene-palladium complexes (introducing the nucleophile at a vinylic rather than an allylic carbon) can also be used.1451... 

Although a metal catalysed decomposition of ethyl diazoacetate was originally described by Silberrad and Roy in 19061, it was to be many years before the value of this type of process for cyclopropanation of alkenes using transition metal catalysts was widely appreciated and reliable, efficient methods were developed. By the early 1960s, the reaction had become important in organic synthesis. Various transition metal compounds have been screened for catalytic cyclopropanation. Copper, rhodium and palladium compounds have... 

Beletskaya, I. P. Bessmertnykh, A. G. Guil-lard, R. Palladium-catalyzed synthesis of aryl-substituted polyamine compounds from aryl halides. Tetrahedron Lett. 1997, 38, 2287-2290. 

Fortunately, most of the palladium addition reactions with olefins can be carried out catalytically in the palladium compound so that large amounts of the expensive palladium compounds are not needed. As in the inorganic palladium salt additions, cupric chloride is a useful reoxidant. This, of course, limits the catalytic reaction to cases where olefin isomerization is not a problem. The cupric chloride is reduced to cuprous chloride during the reaction. As in the acetaldehyde synthesis, the reaction may be made catalytic in copper as well as palladium by adding oxygen and, in this case, hydrogen chloride also. 

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