NAD(P)+-NAD(P)H models. 72. Isotope effects to prove the multi-step mechanism in the reduction with an NAD(P)H analog.
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概要
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Reduction of 1,4-benzoquinone and its various derivatives with 1-benzyl-1,4-dihydronicotinamide (BNAH) and its 4-deuteriated derivative was studied. The kinetic deuterium primary isotope effect (<I>k</I><SUP>H</SUP>⁄<I>k</I><SUP>D</SUP>) for this reaction appears always larger than the isotopic ratio in the product, BNA<SUP>+</SUP>(<I>Y</I><SUP>H</SUP>⁄<I>Y</I><SUP>D</SUP>; product isotope effect). In the absence of magnesium ion, <I>Y</I><SUP>H</SUP>⁄<I>Y</I><SUP>D</SUP> increases as the substrate becomes less electron-demanding. In the presence of magnesium ion which accelerates the reaction, <I>Y</I><SUP>H</SUP>⁄<I>Y</I><SUP>D</SUP> stays small whereas <I>k</I><SUP>H</SUP>⁄<I>k</I><SUP>D</SUP> is not affected. The results reveal that the reaction proceeds with a multi-step mechanism in which the product-determining and rate-determining steps differ each other.
- 公益社団法人 日本化学会の論文
著者
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Ohno Atsuyoshi
Institute For Chemical Research Kyoto Univ.
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MIKATA Yuji
Institute for Chemical Research, Kyoto University
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Goto Mutsuo
Institute for Chemical Research, Kyoto University
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