Abstract : Conditions allowing the C10‐ and C11‐arylations of dibenzo[b,f]azepines via successive palladium‐catalyzed reactions are reported. Using aryl bromides as the aryl source, the C10‐arylation of dibenzo[b,f]azepines is very selective. Then, using benzenesulfonyl chlorides as the aryl source, the second arylation at C11‐position is achieved affording non‐symmetrical C10,C11‐diarylated dibenzo[b,f]azepines. Both reactions tolerate a variety of substituents on the aryl source.
