Nucleophilic addition of organometallics to chiral 1-acylpyridinium salts occurs with high diastereoselectivity to give N-acyl-2,3-dihydro-4-pyridones, which are useful building blocks for the asymmetric synthesis of various alkaloids. The synthetic utility of these heterocycles lies in the ease of preparation and substitution. Our recent efforts at exploring the scope of this chemistry and its application towards the enantioselective synthesis of various alkaloids are described.