Hydroesterification of 2-vinyl-6-methoxynaphthalene using palladium complexes containing chelating nitrogen ligands

Hydroesterification of 2-vinyl-6-methoxynaphthalene (VMN) to methyl ester of 6-methoxy naphthyl propionic acid (ester of naproxen) has been investigated using palladium complexes containing the chelating N∩O and N∩N ligands (pyridine-2-carboxylate, 2-acetylpyridine, 2-pyridine-carboxaldehyde, and bipyridine) as catalysts. Palladium complex containing 2-acetylpyridine as the ligand was found to be superior to other Pd-complexes. Both acid and halide promoters were necessary for high activity and selectivity. As an acid promoter, benzenesulfonic acid was found to be more effective compared to p-toluenesulfonic acid. Formation of ether 2-methoxy-6-(1-methoxyethyl)naphthalene and a polymer of VMN was observed in all the reactions. It was observed that active catalytic species generated during carbonylation reaction was responsible for the polymer formation. The effect of various parameters such as solvents, CO pressure, and alcohols on the catalytic activity as well as the selectivity was investigated. The turnover frequency using the complex Pd(acpy)(PPh3)(OTs)2 (acpy = 2-acetylpyridine) catalyst was found to be 42 h−1, which is the highest for the hydroesterification of VMN.

Graphical abstractPalladium complexes containing chelating N∩O and N∩N were examined in the hydroesterification of 2-vinyl-6-methoxynaphthalene to the ester of naproxen. The acid and halide promoters were required to achieve high activity and selectivity. The effect of various reaction parameters was investigated. The turnover frequency using the complex Pd(acpy)(PPh3)(OTs)2 was found to be 42 h−1.Figure optionsDownload full-size imageDownload as PowerPoint slide