Organic Chemistry

Ring-Opening Hydroarylation of Monosubstituted Cyclopropanes Enabled by Hexafluoroisopropanol



Ring-opening hydroarylation of cyclopropanes is typically limited to substrates bearing a donor-acceptor motif. Here, the transformation is achieved for monosubstituted cyclopropanes by using catalytic Brønsted acid in hexafluoroisopropanol (HFIP) solvent, constituting a rare example where such cyclopropanes engage in intermolecular C–C bond formation. Branched products are obtained when electron-rich arylcyclopropanes react with a broad scope of arene nucleophiles in accord with a simple SN1-type ring-opening mechanism. In constrast, linear products are obtained when cyclopropylketones react with electron-rich arene nucleophiles. In the latter case, mechanistic experiments and DFT-calculations support a homo-conjugate addition pathway.


Thumbnail image of ChemRxivCyclopropanesnonDAv10CNRcopy.pdf

Supplementary material

Thumbnail image of SupportingInformationwithSpectra.pdf
Supporting Information with Spectra
Thumbnail image of TOCv2.tiff
TOC v2