Long-Range C–H Bond Activation by Rh^III-Carboxylates

Traditional C–H bond activation by a concerted metalation–deprotonation (CMD) mechanism involves precoordination of the C–H bond followed by deprotonation from an internal base. Reported herein is a “through-arene” activation of an uncoordinated benzylic C–H bond that is 6 bonds away from a Rh^III ion. The mechanism, which was investigated by experimental and DFT studies, proceeds through a dearomatized xylene intermediate. This intermediate was observed spectroscopically upon addition of a pyridine base to provide a thermodynamic trap.