Inversion of Diastereo- and Enantiofacial Selectivities in the Katsuki-Sharpless Asymmetric Epoxidation of (E)-Alkenylethylene Glycols

Abstract
The Katsuki-Sharpless asymmetric epoxidation of six optically active (S,E)-alkenylethylene glycols 12a-f [(S,E)-3-alkene-1,2-diols] has been examined. The reaction proceeds only in the presence of diisopropyl (L)-(+)-tartrate leading to exclusive formation of syn-epoxides 13a-f [(2R,3S, 4S)-3,4-epoxyalkane-1,2-diols] in good chemical yield with good diastereoselectivities. Interestingly, the reaction occurs with inversion of diastereo- and enantiomeric modes to those expected by the empirical rule established for simple allylic alcohols.

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