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Electrochemical Deconstructive Functionalization of Cycloalkanols via Alkoxy Radicals Enabled by Proton-Coupled Electron Transfer

Mishra Deepak Hareram, Albara A. M. A. El Gehani, James Harnedy, Alex C. Seastram, Andrew C. Jones, Matthew Burns, Thomas Wirth, Duncan L. Browne, Louis C. Morrill

2022Organic Letters37 citationsDOIOpen Access PDF

Abstract

Herein, we report a new electrochemical method for alkoxy radical generation from alcohols using a proton-coupled electron transfer (PCET) approach, showcased via the deconstructive functionalization of cycloalkanols. The electrochemical method is applicable across a diverse array of substituted cycloalkanols, accessing a broad range of synthetically useful distally functionalized ketones. The orthogonal derivatization of the products has been demonstrated through chemoselective transformations, and the electrochemical process has been performed on a gram scale in continuous single-pass flow.

Topics & Concepts

ChemistrySurface modificationElectrochemistryDerivatizationElectron transferProton-coupled electron transferAlkoxy groupCombinatorial chemistryPhotochemistryRadicalProtonElectrodeOrganic chemistryPhysical chemistryAlkylHigh-performance liquid chromatographyQuantum mechanicsPhysicsRadical Photochemical ReactionsCO2 Reduction Techniques and CatalystsCatalytic C–H Functionalization Methods