Mechanism for the reduction of ketones to the corresponding alcohols using supercritical 2-propanol |
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Authors: | Takashi Kamitanaka Tomoko Matsuda |
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Institution: | a Department of Materials Chemistry, Ryukoku University, Seta, Otsu, Shiga 520-2194, Japan b Department of Bioengineering, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8501, Japan |
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Abstract: | The mechanism for the reduction of ketones into the corresponding alcohols using supercritical 2-propanol under non-catalytic conditions was investigated. The studies of the kinetic-isotope effect and isotopic-labeling for the reduction of benzophenone and acetophenone were carried out using (CH3)2CD(OH), (CH3)2CH(OD), (CD3)2CH(OH), and (CD3)2CD(OD). It was clarified that the α- and hydroxyl hydrogens on 2-propanol, respectively, transfer to the carbonyl C and O in the rate-determining step. These isotope studies also suggested that this reaction proceeds via a six-membered cyclic transition state analogous to that of the Meerwein-Ponndorf-Verley reduction. The fact that Hammett's reaction constant for this reaction was low, i.e., ρ=0.33, and that the reduction of the prochiral ketones using optically active alcohols at supercritical or high temperature provided optically active products also supported the existence of a six-membered cyclic transition state. |
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Keywords: | Supercritical alcohol Meerwein-Ponndorf-Verley reduction Kinetic-isotope effect Substituent effect Concerted mechanism |
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