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 language | English (US) |
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Pages (from-to) | 1457-1462 |
Number of pages | 6 |
Journal | Journal of the American Chemical Society |
Volume | 141 |
Issue number | 4 |
DOIs | |
State | Published - Jan 30 2019 |
All Science Journal Classification (ASJC) codes
- General Chemistry
- Biochemistry
- Catalysis
- Colloid and Surface Chemistry