1O2 Mediated Conversion of β-Enaminonitriles to α-Keto Amides Photosensitized by Recyclable H2TPP in Visible Light

Abstract

We report a one-step approach for the conversion of β-enaminonitriles to synthetically versatile α-keto amides in moderate to high yields under visible light irradiation photosensitized by porphyrins. The method is mild, cost-effective, and sustainable and requires air as the sole reagent/oxidant. The reaction is believed to proceed via an ene-type pathway initiated by 1O2, followed by dehydration, imine hydrolysis, and subsequent nucleophilic substitution of the cyanide group by amine. The method offers a broad substrate scope and has also been extended for synthesis of α-keto esters with aliphatic alcohols as nucleophiles. The porphyrin recovered after the reaction can be reused multiple times.