Palladium-catalyzed methods for the aerobic oxidative coupling of alkenes and oxygen nucleophiles (e.g., water and carboxylic acids) have been known for nearly 50 years. The present account summarizes our development of analogous aerobic oxidative amination reactions, including the first intermolecular aza-Wacker reactions compatible with the use of unactivated alkenes. The reactions are initiated by intra- or intermolecular aminopalladation of the alkene. The resulting alkylpalladium(II) intermediate generally undergoes beta-hydride elimination to produce enamides or allylic amide products, but in certain cases, the Pd-C bond can be trapped to achieve 1,2-difunctionalization of the alkene, including carboamination and aminoacetoxylation. Mechanistic studies have provided a variety of fundamental insights into the reactions, including the effect of ancillary ligands on palladium catalysts, the origin of the Brønsted-base-induced switch in regioselectivity in the oxidative amination of styrene, and evidence that both cis- and trans-aminopalladations of alkenes are possible. Overall, these reactions highlight the potential utility of an "organometallic oxidase" strategy for the selective aerobic oxidation of organic molecules.
R-Diimine nickel(II) complexes covalently linked to a silica support were obtained by the reaction of an amino-or hydroxy-functionalized R-diimine nickel complex with silica particles treated with trimethyl aluminum. These silica-supported aryl R-diimine nickel(II) precatalysts linked via an amino (1a) or hydroxy functionality (1b-c) at the p-aryl position, and precatalysts linked via one (2a) or two (2b) hydroxy functionalities in the alkyl backbone were used in slurry polymerizations of ethylene to produce branched polyethylenes. Activation of precatalysts with ethylaluminum sesquichloride was effective even at very low Al/Ni ratios of 48. Initial polymerizations, performed at 60 °C and 150 psig ethylene, showed excellent productivities of up to 10.8 kg PE per gram of 1b (3.0 wt % nickel loading). Low productivities at temperatures above 60 °C can in part be overcome by increase in ethylene pressure. For example, a productivity of 6.0 kg PE per gram of 1b (3.0 wt % nickel loading) was obtained at 80 °C and 700 psig ethylene. The best polymerization productivities were obtained with trimethylaluminum as a traceless silica-linker, however, tetrachlorosilane and trichloroborane are attractive alternatives. Branching densities can be controlled by choice of ortho-aryl substituents. No reactor fouling occurs with these supported catalysts.
Palladium-catalyzed methods for intermolecular aerobic oxidative amination of alkenes have been identified that are compatible with the use of alkene as the limiting reagent. These procedures, which enhance the utility of this reaction with alkenes that are not commercially available, are demonstrated with substrates bearing dialkyl ether, carboxyester, epoxide, and silyl ether groups.
A series of new zirconium dichloride complexes bearing bulky cis-bis (amino) (10), and 2,6-diisopropylphenyl (11)] were prepared in high yields by a twostep synthetic route. The structure of cis-[(Ph 2 CHN)-(tBuNP)] 2 Zr(NMe 2 ) 2 (8a), determined by X-ray analysis, shows that the zirconium atom has a distorted trigonal-bipyramidal configuration consisting of four equidistant metal−amido nitrogen bonds and an additional coordination between the metal and a nitrogen atom from the cyclodi-
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