Rhodium-Catalyzed Intramolecular [3+2+2] Cycloadditions between Alkylidenecyclopropanes, Alkynes, and Alkenes

A Rh‐catalyzed intramolecular [3+2+2] cycloaddition is reported. The cycloaddition affords synthetically relevant 5,7,5‐fused tricyclic systems of type 2 from readily available dienyne precursors. The transformation takes place with moderate or good yields, high diastereoselectivity, and total chemoselectivity. Carbocycle synthesis: A Rh‐catalyzed intramolecular [3+2+2] cycloaddition is reported (see scheme; cod=1,5‐cyclooctadiene, EWG=electron‐withdrawing group). The cycloaddition affords synthetically relevant 5,7,5‐fused tricyclic systems of type 2 from readily available dienyne precursors. The transformation takes place with moderate or good yields, high diastereoselectivity, and total chemoselectivity.