Keyword : Palladium, Catalyzed Alkylation, Olefins.
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Tuesday, May 25, 2010
Palladium-Catalyzed Alkylation of Unactivated Olefins
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Tuesday, May 25, 2010
Abstract
Reaction of a 3-butenyl -diketone with a catalytic amount of PdCl2(CH3CN)2 in dioxane at room temperature led to olefin hydroalkylation and formation of the corresponding 2-acylcyclohexanone in good yield as a single regioisomer. Deuterium-labeling experiments for the hydroalkylation of 7-octene-2,4-dione were in accord with a mechanism involving outer-sphere attack of the pendant enol on a palladium-complexed olefin to form a palladium cyclohexyl species, followed by palladium migration via iterative -hydride elimination/ addition and protonolysis from a palladium enolate complex. In comparison to a 3-butenyl -diketone, reaction of a 4-pentenyl -diketone with a catalytic amount of PdCl2(CH3CN)2 in the presence of CuCl2 led to oxidative alkylation and formation of the corresponding 2-acyl-3-methyl-2-cyclohexenone in good yield as a single isomer.
Unactivated olefins tethered to less reactive carbon nucleophiles such as -keto esters, -aryl ketones, and even dialkyl ketones underwent palladium-catalyzed hydroalkylation in the presence of Me3SiCl or HCl to form the corresponding cyclohexanones in moderate-to-good yield with high regioselectivity.
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