Palladium acetate coupling with

The direct introduction of the two-carbon unit of the heterocyclic ring, ortho to an existing carboxylic acid (ester) can be achieved in two ways ort/io-bromobenzoates can be coupled with 7r-(2-methoxyallyl)nickel bromide for the introduction of acetonyl, or thallation of benzoic acids, ortho to the carboxyl, can be followed by palladium-catalysed coupling with alkenes. Benzoates carrying an ortho acetylenic substituent can be ring closed using mercuric acetate, as shown below." ... 

The analgesic properties of various phenylacetic acids continue to stimultae the development of new routes to compounds of this type. Aryl bromides can be converted directly into phenylacetates by palladium-catalysed coupling with ethyl a-(tri-n-butylstannyl)acetate in the presence of zinc bromide. Aryl iodides can also be directly coupled to the potassium... 

Crowded vinyl triflates conld also be nsed in the cross-coupling reactions (Scheme4.277) [439,440]. This chemistry was attractive since the vinyl triflates could be readily generated from ketones. With the triflates in hand, the catalyst system comprised of palladium acetate along with a flexible diphosphine ligand and an amine as the base was nsed to generate the vinylphosphines. This palladium salt has been used as an air-stable precursor to a... 

Several newer methods take advantage of the highly selective nature of organopaHadium reagents. A palladium acetate-triarylphosphine catalytic system has been employed to induce the coupling of bromobenzene with the desired acrylate ester (13). 

The chemistry of vinyl acetate synthesis from the gas-phase oxidative coupling of acetic acid with ethylene has been shown to be facilitated by many co-catalysts. Since the inception of the ethylene-based homogeneous liquid-phase process by Moiseev et al. (1960), the active c ytic species in both the liquid and gas-phase process has always been seen to be some form of palladium acetate [Nakamura et al, 1971 Augustine and Blitz, 1993]. Many co-catalysts which help to enhance the productivity or selectivity of the catalyst have appeared in the literature over the years. The most notable promoters being gold (Au) [Sennewald et al., 1971 Bissot, 1977], cadmium acetate (Cd(OAc)j) [Hoechst, 1967], and potassium acetate (KOAc) [Sennewald et al., 1971 Bissot, 1977]. 

The Heck coupling reaction appeared to be a route of choice to achieve the synthesis of the modified-DIOP ligands. We previously studied the palladium-catalyzed coupling of acrolein and acrolein acetals with several polyaromatic and heteroaromatic bromides either in the presence of homogeneous or heterogeneous catalytic systems (6, 7). After optimization of the reaction conditions, high conversions and selectivities were achieved except with anthracenyl derivatives (8). Based on these results, we developed the synthesis of the desired ligands. The... 

Arenediazonium chlorides and hydrogen sulfates react with tetram-ethyltin in aqueous acetonitrile in the presence of a catalytic amount of palladium acetate to give high yields of substituted toluenes.130 One-pot hydrostannylation/Stille couplings with catalytic amounts of... 

Another compound 9 with three heterocyclic rings linearly fused (5 5 5) with two heteroatoms has been prepared from 1,1 -carbonyl diindole 297 <2001T5199>. Palladium-mediated coupling of the 2- and 2 -positions of 297 afforded the 1,1 -carbonyl-2,2 -biindolyl 9. 1,1 -Carbonyl diindole 297 was in turn obtained in 41% yield from 1,1 -carbonyldiimidazole 296 by reaction with indole in DMSO at 125 °C. The palladium-catalyzed coupling step afforded the desired product 9 in low yield and required a stoichiometric amount of palladium acetate. Therefore, it was felt prohibitively expensive. Addition of various co-oxidants (Ac20, Mn02, and Cu(OAc)2, etc) to make the reaction catalytic in palladium did not result in any improvement of the yield of 18 (Scheme 53). 

Photothermal decomposition of palladium acetate by scanned cw Ar+ laser irradiation produces metal features that exhibit pronounced periodic structure as a function of laser power, scan speed, substrate and beam diameter, as shown in Figures 3 and 4. The periodic structure is a function of the rate at which the film is heated by absorption of the incident laser radiation coupled with the rate at which the heat of the decomposition reaction is liberated. This coupling generates a reaction front that outruns the scanning laser until quenched by thermal losses, the process to be repeated when the laser catches up and reaches unreacted material. Clearly, such a thermal process is also affected by the thermal conductivity of the substrate, the optical absorption of the substrate in those cases where the overlying film is not fully absorbing,... 

Several palladium catalysts for formation of aryl sulfides from aryl halides have been investigated more recently. A combination of Pd2(dba)3 and DPEphos catalyzed the formation of a broad range of diaryl sulfides in the presence of 1 mol.% palladium and NaO-t-Bu base in toluene solvent.12,rThe highest yields of alkyl aryl sulfides were obtained from aryl triflates and n-butyl thiol catalyzed by a combination of palladium acetate and BINAP. However, these reactions contained 10 mol.% catalyst, were long, and required deactivated aryl triflates. A combination of Pd2(dba)3 and DPPF catalyzed the coupling of thiols with resin-bound aryl halides.121... 

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