Bis-Lewis Acid and Chloride Anion Cooperatively Catalyzed One-Pot Five-Step Cascade toward N -Fused 5/7/6 and 5/6/6 Tricycles

N -Fused 5/7/6 tricyclic scaffold is the core structure of tetrapetalone family alkaloids. Herein, we disclose a strategy for the atom- and step-economic synthesis of N -fused 5/7/6 tricyclic scaffolds via a bis-Lewis acid and chloride cooperatively catalyzed one-pot five-step cascade reaction of o -alkenylaryl isocyanides with α,β-unsaturated carbonyls. The reaction is initiated by a [4 + 1] cycloaddition to form a furan intermediate, which is followed by furan-based [4 + 2] cycloaddition, C–O scission, C–C cleavage, and finally C–N formation. Notably, instead of the conventional [4 + 2] cycloaddition of furan to form a benzene ring, in this domino process, the in situ generated six-membered ring is reopened to create a N -fused 5/7/6 tricyclic framework. Based on the results of control experiments and DFT calculations, both the bis-Lewis acid and the nucleophilic chloride participated in reactivity regulation. Furthermore, this efficient domino transformation could be applied to assemble N -fused 5/6/6 tricycles and the amino analog of (±)-tetrapetalone G.