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Rhodium‐Catalyzed Enantioselective Silylation of Cyclopropyl C−H Bonds
Author(s) -
Lee Taegyo,
Hartwig John F.
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201603153
Subject(s) - enantioselective synthesis , rhodium , silylation , chemistry , enantiomer , intramolecular force , catalysis , bond cleavage , iridium , stereochemistry , medicinal chemistry , organic chemistry
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.