AbstractA route to the eight‐membered nitrogen heterocycles 20a,b is described starting from the 3‐alkyl‐N‐benzylpyridinium salts 14a,b. These azocine derivatives were converted into their respective iminium salts 11 by treatment with methanesulfonic acid. A study concerning the regioselectivity of nucleophilic additions to these salts is presented. Nucleophiles like hydride or Grignard reagents react selectively in the 2‐position to give adducts such as 22 and 23, while azide and phenylthiolate attack the 6‐position to give 24 and 25, respectively. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005)