Ring-Opening Hydroarylation of Monosubstituted Cyclopropanes Enabled by Hexafluoroisopropanol

Abstract

<div><p>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 S<sub>N</sub>1-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.</p></div>

Reply to the Comment on “On the SN2 Reactions Modified in Vibrational Strong Coupling Experiments: Reaction Mechanisms and Vibrational Mode Assignments”

“…In addition to the above considerations, we would like to stress that electronic structure calculations are well-established tools and often play an essential role both in understanding reaction mechanisms and in the interpretation of molecular IR spectra. [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] We would also like to point out that rather than there being "no consensus about the details of the mechanism", each S N 2 reaction has its own intrinsic features, and molecularly detailed calculations are particularly useful to understand these features. [31][32][33][34][35][36][37][38] As already stated in our original work, 2 our results on the reaction mechanism are consistent with the experimentally observed kinetics.…”