Ruthenium Complex-catalyzed Enantiotopos-differentiating Dehydrogenation from Diols

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  • ISHII Youichi
    Department of Synthetic Chemistr y, Faculty of Engineering, The University of Tokyo;
  • SASAKI Ichiro
    Department of Synthetic Chemistr y, Faculty of Engineering, The University of Tokyo;
  • IKARIYA Takao
    Department of Synthetic Chemistr y, Faculty of Engineering, The University of Tokyo;
  • SABURI Masahiko
    Department of Synthetic Chemistr y, Faculty of Engineering, The University of Tokyo;
  • YOSHIKAWA Sadao
    Department of Synthetic Chemistr y, Faculty of Engineering, The University of Tokyo;

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Other Title
  • ルテニウム錯体を触媒とするジオールのエナンチオ場区別脱水素反応
  • ルテニウム サクタイ オ ショクバイ ト スル ジオール ノ エナンチオバ ク

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Description

Ru2Cl4((-)-DIOP)3 (DIOP =2, 2-dimethyl-4, 5-bis(diphenylphosphinomethyl)-1, 3-dioxolane), in the presence of triethylamine, was found to be an efficient catalyst for t h e hydrogen transfer to alkenes from 1, 4- or 1, 5-diols which have the prochiral center or t h e meso structure to afford optically active γ- or δ-lactones with the optical purity up to 16.9 %. This reaction belongs to the enantiotopos-differentiating reaction, in which one of the enantiotopic hydroxymethyl group of prochiral molecules is oxidized to give chiral lactone s. This type of reactions has been rarely reported for homogeneous transition metal complex catalysis, whereas the reactions of the similar type have been extensively investigat e d for enzyme-catalyzed reactions. The chiral induction was directed by the position of the su bstituent(S) of diol, i.e. 3-substituted 1, 5-diols gave (R)-δ-valerolactones and β, β'-dis u bstituted 1, 4- or 1, 5-diols gave γ- or δ-lactones which have S-configuration at the carbon center adjacent to the carbonyl group. It was also found that the two distinct mecha nisms of chiral induction took part in this reaction in a similar manner for the dehyd r ogenation of diols catalyzed by horse liver alcohol dehydrogenase; the first step is the se l ective dehydro. genation of one of the enantiotopic hydroxymethyl groups of a diol to give an optically active hemiacetal, and the second one is the subsequent selective dehydrogenation of one of the epimers of the hemiacetal to give the lactone (kinetic resolution).

Journal

  • NIPPON KAGAKU KAISHI

    NIPPON KAGAKU KAISHI 1985 (3), 465-472, 1985-03-10

    The Chemical Society of Japan

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