A FMO-controlled reaction path in the benzil-benzilic acid rearrangement |
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Authors: | Yamabe Shinichi Tsuchida Noriko Yamazaki Shoko |
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Institution: | Department of Chemistry, Nara University of Education, Takabatake-cho, Nara 630-8528, Japan. yamabes@nara-edu.ac.jp |
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Abstract: | 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 --> R2C(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 C1-C2 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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