This review aims to summarize the recent advances in the field of Cp*MIII (Co, Rh, Ir)‐catalyzed C–H activation followed by subsequent intramolecular reaction. This approach has allowed the synthesis of valuable heterocycles with high structural diversity and complexity, including polycyclic and macrocyclic compounds. In this review, a particular attention has been made to the nature of the coupling partner (alkene, alkyne, etc) and its connection either to the aryl (or vinyl) group or to the directing group. Hence, different types of transformation can occur, involving one or two cyclizations depending on the nature of the directing group. Finally, we discuss some mechanistical aspects (role of the external or internal oxidation, etc) to account for the formation of the cyclic structures.

Spiropiperidine derivatives, an important class of bioactive molecules, were synthesized under mild conditions by rhodium(III)-catalyzed intramolecular ArC-H activation. This reaction provides a novel route to highly substituted tricyclic spiropiperidines in good to excellent yields. Under acidic conditions the resulting enamines reacted with pendant amides to afford spiropiperidines derivatives possessing an original tetracyclic structure.