A novel homogeneous transition-metal catalyst, a polymer-supported terpyridine-palladium(II) complex, was found to promote the aminocarbonylation of aryl iodines using methoxylamine under phosphine-free conditions in water with good yield. The catalyst was recovered and reused several times without loss of catalytic activity. To our knowledge, this is the first example of polymer-supported, palladium-catalyzed synthesis of primary amides by aminocarbonylation of aryl iodides and methoxylamine under phosphine-free conditions in water.
Abstract:A polymer-supported terpyridine palladium complex was prepared. The complex was found to promote hydrodechlorination of aryl chlorides with potassium formate in seawater. Generally, reductive cleavage of aryl chlorides using transition metal catalysts is more difficult than that of aryl bromides and iodides (reactivity: I > Br > Cl); however, the results obtained did not follow the general trend. Therefore, we investigated the reaction inhibition agents and found a method to remove these inhibitors. The polymeric catalysts showed high catalytic activity and high reusability for transfer reduction in seawater.
Primary aromatic amides are valuable compounds, which are generally prepared via Beckmann rearrangement of oximes and the hydration of nitriles in organic solvents. We investigated the environmentally friendly catalytic aminocarbonylation in water. Thus, a novel heterogeneous transition-metal catalyst, a polymer-supported terpyridine-palladium(II) complex, was prepared and found to promote azidocarbonylation of aryl iodides with NaN 3 and to reduce the generated benzoyl azides in water under CO gas to yield primary aryl amides with high to excellent yield in a one-pot reaction. The catalyst was recovered and reused several times with no loss of catalytic activity.
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