Catalytic Enantioselective Access to Planar‐Chiral Macrocyclophanes

Macrocyclophanes are a class of macrocyclic molecules featuring aliphatic ansa chains linking non-adjacent positions of an aromatic ring, which have garnered significant attention due to their extensive applications in biological activity, pharmaceutical research, and selective optical recognition. In this review, it summarizes recent advancements in the catalytic enantioselective synthesis of planar-chiral macrocyclophanes, focusing on various synthetic routes, including: a) transition-metal-catalyzed enantioselective alkyne cyclotrimerization for planar construction; b) (dynamic) kinetic resolution of achiral or prochiral macrocyclophanes; c) enantioselective substitution of aromatic rings; and d) enantioselective macrocyclization for the formation of ansa chains. The aim is to highlight the state-of-the-art advances in catalytic enantioselective construction of planar-chiral macrocyclophanes and to push this field toward new horizons.