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Tunable System for Electrochemical Reduction of Ketones and Phthalimides

Yaxin Wang, Jianyou Zhao, Tianjiao Qiao, Jian Zhang, Gong Chen

2021Chinese Journal of Chemistry39 citationsDOI

Abstract

Main observation and conclusion Herein, we report an efficient, tunable system for electrochemical reduction of ketones and phthalimides at room temperature without the need for stoichiometric external reductants. By utilizing NaN 3 as the electrolyte and graphite felt as both the cathode and the anode, we were able to selectively reduce the carbonyl groups of the substrates to alcohols, pinacols, or methylene groups by judiciously choosing the solvent and an acidic additive. The reaction conditions were compatible with a diverse array of functional groups, and phthalimides could undergo one‐pot reductive cyclization to afford products with indolizidine scaffolds. Mechanistic studies showed that the reactions involved electron, proton, and hydrogen atom transfers. Importantly, an N 3 /HN 3 cycle operated as a hydrogen atom shuttle, which was critical for reduction of the carbonyl groups to methylene groups.

Topics & Concepts

ChemistryPhthalimidesMethyleneElectrochemistryImideSelective reductionAllylic rearrangementHydrogen atomSolventPhotochemistryCombinatorial chemistrySupporting electrolyteOrganic chemistryPhthalimideGroup (periodic table)CatalysisPhysical chemistryElectrodeRadical Photochemical ReactionsCatalytic C–H Functionalization MethodsCO2 Reduction Techniques and Catalysts
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