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Decarboxylative/Oxidative Amidation of Aryl α-Ketocarboxylic Acids with Nitroarenes and Nitroso Compounds in Aqueous Medium

Dinesh S. Barak, Dipak J. Dahatonde, Shashikant U. Dighe, Ruchir Kant, Sanjay Batra

2020Organic Letters25 citationsDOI

Abstract

The decarboxylative/oxidative amidation of aryl α-ketocarboxylic acids with 5-aryl-3-nitroisoxazole-4-carboxylates and substituted dinitrobenzenes under oxidative aqueous conditions to afford N-aryl amides is described. The reaction is suggested to proceed via a radical pathway in which a benzoyl nitroxyl radical, the key intermediate formed from reaction between nitroarene and benzoyl radical from glyoxalic acid, couples with hydroxyl radical from water to produce amide. Mechanistic insight allowed the scope of the strategy to be expanded to the synthesis of amides via reaction between aryl α-ketocarboxylic acids and nitroso compounds.

Topics & Concepts

ChemistryArylAmideNitrosoOxidative phosphorylationRadicalNitroso CompoundsNitroxylOrganic chemistryAqueous mediumAqueous solutionCombinatorial chemistryMedicinal chemistryBiochemistryAlkylRadical Photochemical ReactionsSulfur-Based Synthesis TechniquesSynthesis and Catalytic Reactions
Decarboxylative/Oxidative Amidation of Aryl α-Ketocarboxylic Acids with Nitroarenes and Nitroso Compounds in Aqueous Medium | Litcius