Palladium‐Catalyzed Heck/Insertion/Decarboxylation Domino Sequence: Synthesis of Dihydrocyclohepta[de]naphthalenes

A Pd‐catalyzed cascade cyclization for the construction of fused dihydrocyclohepta[de]naphthalene skeletons was developed. The skeleton was assembled from 3‐iodo‐4H‐chromen‐4‐one, norbornene and 8‐bromo‐1‐naphthoic acid. Unlike the classic Catellani reaction, which involves the removal of norbornene, in the present system, norbornene acts as a building block for the construction of rigid nonplanar molecular architectures rather than as an ortho‐directing transient mediator. This synthesis involves the formation of three C−C bonds via a one‐pot process, and it is compatible of a series of substituents.