Rhodium‐Catalyzed Regioselective <italic>Ortho</italic> C−H Olefination of 2‐Arylindoles via NH‐Indole‐Directed C−H Bond Cleavage.

Abstract: In the past decades, C−H oxidative olefination of indole at C‐2, C‐3, C‐4 and C‐7 positions was well addressed. We report here a rhodium‐catalyzed NH‐indole‐directed <italic>ortho</italic> C−H bond olefination of 2‐arylindoles. This cross‐dehydrogenative‐coupling proved to be broad in substrate scope, tolerating a variety of functional groups. The synthesis of 6<italic>H</italic>‐isoindolo[2,1‐α]indoles via rhodium‐catalyzed <italic>ortho</italic> C−H olefination and subsequent intramolecular aza‐Michael reaction of 2‐arylindoles was also demonstrated. [ABSTRACT FROM AUTHOR]