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

研究成果: Article

14 引用 (Scopus)

抄録

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.

元の言語English
ページ(範囲)1457-1462
ページ数6
ジャーナルJournal of the American Chemical Society
141
発行部数4
DOI
出版物ステータスPublished - 2019 1 30
外部発表Yes

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Isomerization
Oxidation-Reduction
Alcohols
Light
Carbonyl compounds
Excited states
Protons
Chemical activation
Electrons
Hydrogen
alkoxyl radical

ASJC Scopus subject areas

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

これを引用

A Redox Strategy for Light-Driven, Out-of-Equilibrium Isomerizations and Application to Catalytic C-C Bond Cleavage Reactions. / Ota, Eisuke; Wang, Huaiju; Frye, Nils Lennart; Knowles, Robert R.

:: Journal of the American Chemical Society, 巻 141, 番号 4, 30.01.2019, p. 1457-1462.

研究成果: Article

Ota, Eisuke ; Wang, Huaiju ; Frye, Nils Lennart ; Knowles, Robert R. / A Redox Strategy for Light-Driven, Out-of-Equilibrium Isomerizations and Application to Catalytic C-C Bond Cleavage Reactions. :: Journal of the American Chemical Society. 2019 ; 巻 141, 番号 4. pp. 1457-1462.
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