Directing-Group-Assisted Transition-Metal-Catalyzed Direct Intermolecular C−H Amidation and Amination of Arenes

This review focuses on the most recent advances in the field of transition‐metal‐catalyzed direct intermolecular C−H amidation and amination of arenes. The manuscript is divided into two parts according to whether or not external oxidants are required. The first part includes the cases of simple neutral amines, amides, or sulfonamides in combination with external oxidants. The second section contains the examples of preactivated amino sources in the absence of any external oxidants. In each part, the content is classified in line with the different types of transition‐metal catalysts used, including Rh, Ru, Ir, Pd, Cu, Ni, Co, and Fe. In addition, the substrate scope and limitations as well as catalytic mechanism are discussed. Amidation and amination: Recent advances in the field of transition‐metal‐catalyzed direct intermolecular C−H amidation and amination of arenes are summarized. There are generally two types of reaction models. The first kind employs simple neutral amines, amides, or sulfonamides in combination of external oxidants. The second class utilizes preactivated amino sources in the absence of any external oxidants.