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

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 ?-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.

SUBMITTER: Ota E

PROVIDER: S-EPMC6508595 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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

Ota Eisuke E Wang Huaiju H Frye Nils Lennart NL Knowles Robert R RR

Journal of the American Chemical Society 20190115 4

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 me ...[more]

PMID: 30628777

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