Abstract: | Substituted cyclopentab]indoles are selectively brominated in good yields with excess pyridine ‐ Br2 charge‐transfer complex (PyBr2) in a one‐pot reaction to provide 5 and/or 7‐bromoindoles. The mechanism involves the formation of an adduct (addition of bromine on the central double bond) which is subsequently reduced in situ with Zn and AcOH. A variety of functional groups in the cyclopentyl and the benzenoid rings are tolerated. |