Electrochemical Iodination-Triggered Skeletal Rearrangement of Acryl Imides via Cascade Substitutions to Access α,β-Dihydroxyl Amides

Abstract

Electrochemical rearrangement reactions represent one of the most versatile types of organic chemical transformations, which afford efficient strategies for the rapid construction of complex molecular skeletons. However, known achievements in electrochemical rearrangement of alkene compounds are mainly focused on the migration of radical species. Thus, the development of new electrochemical rearrangement modes, in particular, remote migration rearrangement, is in high demand but still remains a great challenge. Herein, we report a novel electrochemical rearrangement reaction of acryl imides in the presence of nBu₄NI and water, which proceeds via nucleophilic substitutions leading to skeletal editing and affording α,β-dihydroxyl amides with up to 76% yield. Control experiments suggest that this reaction proceeds through oxidation of iodide anion, iodination of alkenyl bond, coupling with water, substitution to form epoxide, substitution ring-opening, and intramolecular substitution to afford the desired dihydroxyl amides. This work represents a new electrochemical rearrangement mode and provides a new and efficient strategy for the synthesis of α,β-dihydroxyl amide derivatives.

Keywords

Electrochemical reactions / Rearrangement reactions / Alkenes / Iodination / Acryl imides / Skeletal editing / Green chemistry / Cross-coupling / Substitution

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2025 SIOC, CAS, Shanghai, & WILEY-VCH GmbH