One‐step Annulation/Chlorination towards Chlorinated Diphenanthro, Dibenzophenanthro, and Dichrysenothiophens

One‐step Scholl and chlorination reactions on fourteen polyaryl thiophenes offered regioselective preparations of chlorinated diphenanthro‐, dibenzophenanthro‐, dichrysenothiophenes derivatives. Specific annulating patterns and the positions of chlorination in these polyheteroaromatics were confirmed by single‐crystal X‐ray analyses for the selected ones. Despite being twisted in their molecular frameworks, these derivatives packed into near‐perfect face‐to‐face styles. Present work reports one‐step regioselective Scholl and chlorination reactions on fourteen polyarylthiophenes, using iron chloride. These reactions afforded pure chlorinated diphenanthro‐, dibenzophenanthro‐, dichrysenothiophenes derivatives.