Synthesis of Benzo[3,4]azepino[1,2‐ <i>a</i> ]indoles via Rh (III)‐Catalyzed <i>NH</i> ‐Indole‐Directed C‐H/N‐H [4+3] Annulation of 2‐Phenylindoles With Methyleneoxetanones

ABSTRACT A regioselective rhodium‐catalyzed NH ‐indole‐directed C–H coupling of 2‐arylindoles with methyleneoxetanones, followed by TsCl/DMAP‐mediated intramolecular amidation leading to biologically relevant benzo[3,4]azepino[1,2‐ a ]indoles bearing a fused seven‐membered ring is presented. Excellent functional group tolerance is demonstrated, yielding diverse indole‐fused seven‐membered‐ring architectures and providing gramme quantities of products through scalability.