Intramolecular (4+3) Cycloadditions of Oxidopyridinium Ions: Towards Daphnicyclidin A

N-alkylation of 5-hydroxynicotinic acid esters with electrophiles containing diene functionality produces salts that undergo intramolecular (4+3) cycloaddition reactions upon heating in the presence of base. Initial studies used a three-carbon tether to join the pyridinium ion and diene, revealing some aspects of the inherent selectivity of the reaction with such substrates. Much more challenging was the synthesis of related species possessing only a two-carbon tether. Nevertheless, the cycloaddition of such compounds was successful, leading directly to the ABC ring system of the alkaloid daphnicyclidin A.