Abstract A gold‐catalyzed tandem cyclization of o ‐phenylenediamines with ynones to synthesize benzo[ b ]indeno[1,2‐ e ][1,4]diazepine has been developed. The mechanism was explored by control experiments. The method provides a way to access a range of benzo[ b ]indeno[1,2‐ e ][1,4]diazepine derivatives in diversity‐oriented synthesis aiming at discovering structurally diverse scaffolds. magnified image