Synthesis of new azocine derivatives and their functionalization by nucleophilic addition to their iminium salts

A 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)

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