Rhodium‐Catalyzed Regioselective Carboacylation of Olefins: A CC Bond Activation Approach for Accessing Fused‐Ring Systems

Cut and sew: A rhodium-catalyzed regioselective carboacylation reaction of benzocyclobutenones was developed (see scheme). Directed by the pendant olefins, the C1C2 bond is selectively cleaved rather than the C1C8 bond. Subsequent alkene insertion leads to complex fused-ring systems. This reaction provides facile access to natural-product-like polycyclic structures in a chemoselective and atom-economic fashion.