Beyond Directing Groups: Transition-Metal-Catalyzed C-H Activation of Simple Arenes

The use of coordinating moieties as directing groups for the functionalization of aromatic C?H bonds has become an established tool to enhance reactivity and induce regioselectivity. Nevertheless, with regard to the synthetic applicability of C?H activation, there is a growing interest in transformations in which the directing group can be fully abandoned, thus allowing the direct functionalization of simple benzene derivatives. However, this approach requires the disclosure of new strategies to achieve reactivity and to control selectivity. In this review, recent advances in the emerging field of non-chelate-assisted C?H activation are discussed, highlighting some of the most intriguing and inspiring examples of induction of reactivity and selectivity.