Controlling the chemo‐ and regioselectivity of transition‐metal‐catalyzed C−C activation remains a great challenge. The transformations of benzocyclobutenones (BCBs) usually involve the cleavage of C1−C2 bond. In this work, an unprecedented highly selective cleavage of C1−C8 bond with the insertion of alkynes is achieved by using blocking strategy via Ni catalysis, providing an efficient method for synthesis of 1,8‐disubstituted naphthalenes. Notably, the blocking group could be readily removed after the transformation.

Controlling the chemo‐ and regioselectivity of transition‐metal‐catalyzed C−C activation remains a great challenge. The transformations of benzocyclobutenones (BCBs) usually involve the cleavage of C1−C2 bond. In this work, an unprecedented highly selective cleavage of C1−C8 bond with the insertion of alkynes is achieved by using blocking strategy via Ni catalysis, providing an efficient method for synthesis of 1,8‐disubstituted naphthalenes. Notably, the blocking group could be readily removed after the transformation.