Rh(I)‐Catalyzed [4+3]/[4+1] Cycloaddition of Diene‐Vinylcyclopropanes and Carbon Monoxide to Access Angular 5/7/5 Tricycles

Abstract Report here is a Rh‐catalyzed [4+3]/[4+1] cycloaddition of diene‐vinylcyclopropanes (diene‐VCPs) and carbon monoxide to access compounds with angular 5/7/5 tricyclic skeleton found in natural products. The reaction has broad scope and further transformation of the [4+3]/[4+1] cycloadduct was also investigated. How this [4+3]/[4+1] reaction occurs and why its competing [4+3] reaction is disfavored have been investigated computationally.