Palladium acetate stoichiometric quantities

Dialkylindolines and 1,3-dialkylindoles are formed in poor yield (<10%) from the reaction of ethyl- or phenymagnesium bromide with 2-chloro-N-methyl-N-allylaniline in the presence of catalytic quantities of (bistriphenylphosphine)nickel dichloride.72 In a modification of this procedure, the allyl derivatives can be converted by stoichiometric amounts of tetrakis(triphenylphosphine)nickel into 1,3-dialkylindoles in moderate yield72 (Scheme 43) an initial process of oxidative addition and ensuing cyclization of arylnickel intermediates is thought to occur. In contrast to the nickel system,72 it has proved possible to achieve the indole synthesis by means of catalytic quantities of palladium acetate.73 It is preferable to use... 

Fujiwara and Moritoni carried out seminal work in the area of C-H alkenylation they reported that palladium(II) complexes could mediate the coupling of unfunctionalized arenes with olefins in refluxing acetic acid [64]. The initial reactions used stoichiometric quantities of palladium salts however the reaction was subsequently... 

Pd -catalyzed aerobic oxidations of alkenes with nucleophiles other than water have met with limited success. Most successful reactions utilize nucleophiles that also serve as solvent such as alcohols and acetic acid. In contrast, the use of a heteroatom or carbon nucleophile generally requires stoichiometric quantities of palladium or the secondary oxidant, often Cu salts. Oxidation of alkenes in alcohols with Pd salts in the presence of a base can afford an acetal or a vinyl ether. Alkoxypalladation, which is the first step in both cases, can be followed by 1,2-hydride shift and attack of alkoxide anion on the resulting oxonium cation, affording the corresponding acetal (eq 5, path a). Formation of the vinyl ether can be understood by p elimination of the palladation intermediate (path b). The acetal of acetaldehyde is the main product in the oxidation of ethylene (R = H) while j8-H ehmination is the main path with higher alkenes. 

Copper-catalyzed C-O, C-N, and C-S Coupling. While there is an extensive variety of palladium catalysts for C(aryl)-X bond formation (X = 0, N, and S), copper corrqtlexes have recently gained renewed popularity in these coupling processes. Use of the (CuOTf)2. benzene complex allows the formation of diaryl ethers from aryl bromides or iodides and phenols in very good yields (76-93%) (eq 121). The reaction occurs in toluene in the presence of cesium carbonate as the base and a catal)4ic quantity of ethyl acetate whose role is probably to increase the solubility of the copper species. In the case of less reactive phenols, yields can be increased by the addition of a stoichiometric amount of carboxylic acid. A slight modification of these conditions has been used in the key diaryl ether formation in the synthesis of verbenachalcone. ... 

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