Rhodium‐Catalyzed Enantioselective Silylation of Cyclopropyl C−H Bonds

Abstract 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 ( S )‐DTBM‐SEGPHOS. The resulting enantioenriched oxasilolanes are suitable substrates for the Tamao–Fleming oxidation to form cyclopropanols with conservation of the ee 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.