Dylan J Abrams, Mathew R Johnson, Caitlin R Lacker, Tehshik P Yoon, Joseph R Martinelli, Shannon S Stahl
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Mediated Electrochemical Oxidation of Nucleosides to Their 5'-Carboxylic Acid Derivatives.
Nucleoside 5'-carboxylic acids are important synthetic targets, but most existing methods to access these compounds use (super)stoichiometric chemical oxidants to oxidize the primary alcohol. The present study introduces an aminoxyl-mediated electrochemical method for oxidation of nucleosides and ribosugars to afford their 5'-carboxylic acid derivatives. The optimized conditions employ 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl (ACT) as the aminoxyl mediator in a water/acetonitrile solvent mixture with tetraethylammonium bicarbonate or monohydrogen phosphate as a base within an undivided electrolysis cell. The reaction tolerates diverse functionality at the nucleobase and sugar positions and is showcased in the oxidation of 10 different substrates, including a 10 g scale oxidation of 2'-O-methylcytidine.
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Chemistry—A European Journal is a truly international journal with top quality contributions (2018 ISI Impact Factor: 5.16). It publishes a wide range of outstanding Reviews, Minireviews, Concepts, Full Papers, and Communications from all areas of chemistry and related fields.
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