Carboxylic Acids as Directing Groups for C−H Bond Functionalization

The selective transformation of C−H bonds is one of the most desirable approaches to creating complexity from simple building blocks. Several directing groups are efficient in controlling the regioselectivity of catalytic C−H bond functionalizations. Among them, carboxylic acids are particularly advantageous, since they are widely available in great structural diversity and at low cost. The carboxylate directing groups can be tracelessly cleaved or may serve as the anchor point for further functionalization through decarboxylative couplings. This Minireview summarizes the substantial progress made in the last few years in the development of reactions in which carboxylate groups direct C−H bond functionalizations with formation of C−C, C−O, C−N, or C−halogen bonds at specific positions. It is divided into sections on C−C, C−O, C−N, and C−halogen bond formation, each of which is subdivided by reactions and product classes. Particular emphasis is placed on methods that enable multiple derivatizations by combining carboxylate‐directed C−H functionalization with decarboxylative couplings. The award for best director goes to…: This Minireview summarizes the substantial progress made in the last few years in the development of reactions in which carboxylate groups direct C−H functionalizations with formation of C−C, C−O, C−N, or C−halogen bonds at specific positions. It is divided into sections on C−C, C−O, C−N, and C−halogen bond formation, each subdivided by reactions and product classes.