Nickel‐Catalyzed Chemo‐, Regio‐ and Diastereoselective Bond Formation through Proximal C?C Cleavage of Benzocyclobutenones

The first catalytic intermolecular proximal C1 C2 cleavage of benzocyclobutenones (BCB) without prior carbonyl activation or employing noble metals has been developed. This protocol operates at room temperature and is characterized by an exquisite chemo‐, regio‐ and diastereoselectivity profile, constituting a unique platform for preparing an array of elusive carbocyclic skeletons.