Taming the Flexible Eight‐Membered Ring: Enantioselective Synthesis of Inherently Chiral Dibenzo[ <i>a</i> , <i>e</i> ]cyclooctatetraenes Enabled by Pd‐Catalyzed Suzuki–Miyaura Cross‐Coupling

ABSTRACT Inherently chiral molecules generated by the curvature of planar frameworks represent an emerging class of three‐dimensional chiral architectures, yet their catalytic asymmetric synthesis remains highly challenging. Herein, we report a Pd‐catalyzed asymmetric Suzuki–Miyaura coupling for the efficient construction of inherently chiral dibenzo[ a , e ]cyclooctatetraene (dbCOT) diene ligands. This strategy enables rapid access to a diverse range of cyclic diene scaffolds with excellent enantioselectivities (up to 98% ee). Mechanistic investigations reveal that the stereochemical outcome is governed by a sequential dynamic kinetic asymmetric transformation (DyKAT) and enantioenrichment process involving two consecutive coupling events. The resulting inherently chiral dbCOT ligands readily coordinate with transition metals and exhibit excellent catalytic performance in Rh‐catalyzed asymmetric additions and Pd‐catalyzed atroposelective transformations. This work establishes a catalytic platform for the synthesis of inherently chiral cyclic diene ligands and expands the toolbox of asymmetric catalysis.