Abstract: | Despite recent progress in the catalytic transformation of inert phenol derivatives as alternatives to aryl halides and triflates, attempts at the cross‐coupling of inert phenol derivatives with the C−H bonds of arenes have met with limited success. Herein, we report the rhodium‐catalyzed cross‐coupling of aryl carbamates with arenes bearing a convertible directing group. The key to success is the use of an in situ generated rhodium bis(N‐heterocyclic carbene) species as the catalyst, which can promote activation of the inert C(sp2)−O bond in aryl carbamates. |