α-(3-Pyridyl)malonates: preparation and synthetic applications

Alkylation of aromatic rings is a major challenge in organic syntheses since more complex carbon skeletons can be constructed. The alkylation of pyridine by nucleophilic aromatic substitution of the nitro group in methyl 3-nitro-4-pyridylcarboxylate (1) with malonic ester is reported. The versatility of the α-(3-pyridyl) malonic ester product (3) is demonstrated by the formation of a number of new 3-alkylated pyridines and new fused bis-heterocycles. cis 2-Halomethyl-4-(3-pyridyl)tetrahydrofuran products were selectively prepared. Exact 1H and 13C NMR assignments of practically all products were obtained by a series of NMR experiments.