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In the reaction of Pd-catalyzed decarboxylative allylic alkylation of ketones to generate tertiary centers, the reaction mechanisms of allyl enol carbonates and that of allyl β-keto esters may be different: Intermediate I from enol carbonates can only undergo decarboxylation to afford Pd enolate II which recombines to the product. Intermediate III from β-keto esters, however, may undergo a facile H-shift to generate IV depending on the acidity of the α-proton. IV recombines to a β-keto acid V, which decarboxylates to the product. Therefore, allyl β-keto esters cannot completely replace enol allyl carbonates in this reaction. See: (a) Tsuji, J, Minami, I. Acc. Chem. Res. 1987, 20, 140
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In the reaction of Pd-catalyzed decarboxylative allylic alkylation of ketones to generate tertiary centers, the reaction mechanisms of allyl enol carbonates and that of allyl β-keto esters may be different: Intermediate I from enol carbonates can only undergo decarboxylation to afford Pd enolate II which recombines to the product. Intermediate III from β-keto esters, however, may undergo a facile H-shift to generate IV depending on the acidity of the α-proton. IV recombines to a β-keto acid V, which decarboxylates to the product. Therefore, allyl β-keto esters cannot completely replace enol allyl carbonates in this reaction. See: (a) Tsuji, J.; Minami, I. Acc. Chem. Res. 1987, 20, 140.
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Chemical Equation Presented
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For reference concerning the much better reactivity of acylimidazolium salts than the corresponding imidazolides, see: (a) Anders, E.; Will, W. Tetrahedron Lett. 1978, 41, 3911.
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