Stereoselective Synthesis of Pyrroloquinolines by a Brønsted Acid Catalyzed [4+2]-Heterocyclization of Indole-7-Carbaldehydes, Anilines and Electron-Rich Alkenes

The pyrrolo[3,2,1‐ij]quinoline heterocyclic core is found in the structure of a variety of compounds with interesting applications and then, new efficient and flexible strategies to construct this skeleton are required. Here, a new diastereoselective tetrafluoroboric acid (HBF4)‐catalyzed three‐component coupling reaction of 1H‐indole‐7‐carbaldehyde derivatives, anilines and electron‐rich alkenes to give pyrrolo[3,2,1‐ij]quinolines is described. The reaction involves an unusual [4+2]‐heterocyclization between an in situ formed imine and an alkene. The new catalytic method, where water is the only by‐product, is efficient, robust and flexible, and allows for multigram‐scale synthesis.