Chemodivergent synthesis of indeno[1,2-]indoles and isoindolo[2,1-]indoles from the same starting materials involving radical cross-dehydrogenative couplings have been developed. Mn(OAc)·2HO selectively promoted an intramolecular radical C-H/C-H dehydrogenative coupling reaction to provide indeno[1,2-]indoles, while an intramolecular radical C-H/N-H dehydrogenative coupling reaction could proceed via electrochemistry to deliver isoindolo[2,1-]indoles. Plausible mechanisms of the chemodivergent reactions were proposed.
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