Aldehyde–Olefin Couplings via Sulfoxylate-Mediated Oxidative Generation of Ketyl Radical Anions

Zhihang Li, Joseph Tate, Adam Noble*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

Abstract

Ketyl radicals are valuable reactive intermediates because they allow carbonyl chemistry to be extended beyond traditional electrophilic reactivity through simple single-electron reduction to a nucleophilic radical. However, this pathway is challenging due to the large negative reduction potentials of carbonyls, thus requiring highly reducing conditions. Herein, we describe the development of an alternative strategy to access ketyl radicals from aldehydes, which avoids the reduction pathway by instead proceeding via single-electron oxidation and desulfination of α-hydroxy sulfinates. These redox-active aldehyde adducts are generated in situ through the addition of sulfoxylate (SO22–) to aldehydes and possess low oxidation potentials, thereby facilitating ketyl radical formation and circumventing the need for strongly reducing conditions. We demonstrate the application of this sulfoxylate-mediated ketyl radical formation in ketyl–olefin coupling reactions.
Original languageEnglish
Pages (from-to)26616-26621
Number of pages6
JournalJournal of the American Chemical Society
Volume146
Issue number39
Early online date20 Sept 2024
DOIs
Publication statusE-pub ahead of print - 20 Sept 2024

Bibliographical note

Publisher Copyright:
© 2024 The Authors. Published by American Chemical Society.

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