Regioselective Construction of Indolylated Cyclic Tetrasubstituted Carbon Centers through Brønsted Acid‐Catalyzed Dearomative Skeletal Rearrangement of Azofurans

Abstract A Brønsted acid‐catalyzed dearomative skeletal rearrangement of azofurans with indoles is reported, enabling a regioselective 1,6‐addition, ring‐opening and 1,4‐addition cascade to produce 26 examples of indolylated pyrrol‐2‐ones with a cyclic tetrasubstituted stereocenter in 58–94% yields. This protocol demonstrates remarkable compatibility regarding azofurans and indoles with different substitution patterns, featuring complete regioselectivity.