Journal
JOURNAL OF ORGANIC CHEMISTRY
Volume 71, Issue 5, Pages 1777-1783Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jo051862r
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Reaction paths for the title rearrangement along with its methyl analogue were investigated by density functional theory calculations. The reaction model is R-CO-CO-R + OH-(H2O)(4) -> RC(OH)-COO- + (H2O)(4) (R = Me and Ph), where the water tetramer is employed both for solvation to OH- and for the proton relay along hydrogen bonds. The reaction is composed of OH- addition, C-C rotation, carbanion [1,2] migration, and proton relay toward the product anions. The rate-determining step was calculated to be the carbanion migration. Apparently, carbanion [1,2] migration is unlikely relative to the carbonium ion one. However, LUMOs of the 1,2-diketones have large and nodeless lobes at the reaction center, the C(1)-C(2) bond. The specific LUMO character is reflected both in the [2+ 1]-like one-center nucleophilic addition and in the carbanion [1,2] shift. The proton relay involved in the isomerization from the oxo intermediate to the carboxylate was calculated to take place via the water tetramer.
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