Aryl palladium complexes react with nitriles to give the imine addition product, which hydrolyses in an acidic aqueous solution forming the corresponding aryl ketone. Aryl palladium precursors include boronic acids, carboxylic acids and sulfinates. Through palladium(II) catalyzed addition of these compounds to β-cyano phosphonate esters, β-keto phosphonate esters are accessible. This group of compounds are interesting substrates in the Horner-Wadsworth-Emmons reaction and serves as a starting point for the synthesis of novel DXR inhibitors. Also, an adapted protocol for Pd(II)-catalyzed desulfitative synthesis of aryl ketones from sodium aryl sulfinates and nitriles in continuous flow has been developed. The title reaction constitutes an interesting model system for use in continuous flow microwave assisted organic synthesis (CF-MAOS) as the use of certain nitriles results in a biphasic reaction mixture.

Synthesis of aryl ketones and β–keto phosphonates by palladium(II) catalyzed addition reactions to nitriles

252nd National Meeting (2016)

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