Site‐Selective C(sp3)−H and C(sp2)−H Functionalization of Amines Using a Directing‐Group‐Guided Strategy

Amines represent an important class of industrial feedstock as many pharmaceuticals, agrochemicals, petrochemicals, and healthcare products are derived from them. Researchers are developing methodologies for the functionalization of aliphatic and aromatic amines by improving their functional‐group tolerance, regioselectivity, chemoselectivity, and time efficiency. Among the most studied methods for the derivatization of amines, C−H activation is gaining significant interest due to easy‐to‐follow, environmentally friendly, and time‐economic protocols. Transition‐metal‐catalyzed C(sp3)−H and C(sp2)−H activation is a fascinating field of chemistry where the electronics of the structure, functional group characteristics, and nature of the directing group (DG) decide the outcome of the chemical reaction. Under carefully tailored reaction conditions and by a selection of the correct substrates/reagent, site‐specific C−H functionalization can be achieved at different positions with respect to the amine group. This review provides an overview of the combination of carbon‐carbon and carbon‐heteroatom functionalizations and describes recent state‐of‐the‐art methodologies, as well as challenges in this emerging field.