A Redox Strategy for Light-Driven, Out-of-Equilibrium Isomerizations and Application to Catalytic C-C Bond Cleavage Reactions

Eisuke Ota, Huaiju Wang, Nils Lennart Frye, Robert R. Knowles

Research output: Contribution to journalArticle

27 Citations (Scopus)

Abstract

We report a general protocol for the light-driven isomerization of cyclic aliphatic alcohols to linear carbonyl compounds. These reactions proceed via proton-coupled electron-transfer activation of alcohol O-H bonds followed by subsequent C-C β-scission of the resulting alkoxy radical intermediates. In many cases, these redox-neutral isomerizations proceed in opposition to a significant energetic gradient, yielding products that are less thermodynamically stable than the starting materials. A mechanism is presented to rationalize this out-of-equilibrium behavior that may serve as a model for the design of other contrathermodynamic transformations driven by excited-state redox events.

Original languageEnglish
Pages (from-to)1457-1462
Number of pages6
JournalJournal of the American Chemical Society
Volume141
Issue number4
DOIs
Publication statusPublished - 2019 Jan 30
Externally publishedYes

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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