Rhodium‐Catalyzed Enantioselective Silylation of Cyclopropyl C−H Bonds

  • Taegyo Lee
    Department of Chemistry University of California Berkeley CA 94720 USA
  • John F. Hartwig
    Department of Chemistry University of California Berkeley CA 94720 USA

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<jats:title>Abstract</jats:title><jats:p>Hydrosilyl ethers, generated in situ by the dehydrogenative silylation of cyclopropylmethanols with diethylsilane, undergo asymmetric, intramolecular silylation of cyclopropyl C−H bonds in high yields and with high enantiomeric excesses in the presence of a rhodium catalyst derived from a rhodium precursor and the bisphosphine (<jats:italic>S</jats:italic>)‐DTBM‐SEGPHOS. The resulting enantioenriched oxasilolanes are suitable substrates for the Tamao–Fleming oxidation to form cyclopropanols with conservation of the <jats:italic>ee</jats:italic> value from the C−H silylation. Preliminary mechanistic data suggest that C−H cleavage is likely to be the turnover‐limiting and enantioselectivity‐determining step.</jats:p>

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