American Chemical Society
ja508367m_si_001.pdf (15.37 MB)

Long-Range C–H Bond Activation by RhIII-Carboxylates

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journal contribution
posted on 2014-10-22, 00:00 authored by Matthew E. O’Reilly, Ross Fu, Robert J. Nielsen, Michal Sabat, William A. Goddard, T. Brent Gunnoe
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 RhIII 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.