Accessing Remote meta‐ and para‐C(sp2)−H Bonds with Covalently Attached Directing Groups

Directing group assisted ortho-C-H activation has been known for the last few decades. In contrast, extending the same approach to achieve activation of the distal meta- and para-C-H bonds in aromatic molecules remained elusive for a long time. The main challenge is the conception of a macrocyclic transition state, which is needed to anchor the metal catalyst close to the target bond. Judicious modification of the chain length, the tether linkage, and the nature of the catalyst-coordinating donor atom has led to a number of successful studies in the last few years. This Review compiles the significant achievements made in this field of both meta- and para-selectivity using covalently attached directing groups, which are systematically classified on the basis of their mode of covalent attachment to the substrate as well as their chemical nature. This Review aims to create a more heuristic approach for recognizing the suitability of the directing groups for use in future organic transformations.