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

14 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

Fingerprint

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

Cite this

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.

In: Journal of the American Chemical Society, Vol. 141, No. 4, 30.01.2019, p. 1457-1462.

Research output: Contribution to journalArticle

@article{af7a387d3aaa4ec78f27d094d20f0a28,
title = "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 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.",
author = "Eisuke Ota and Huaiju Wang and Frye, {Nils Lennart} and Knowles, {Robert R.}",
year = "2019",
month = "1",
day = "30",
doi = "10.1021/jacs.8b12552",
language = "English",
volume = "141",
pages = "1457--1462",
journal = "Journal of the American Chemical Society",
issn = "0002-7863",
publisher = "American Chemical Society",
number = "4",

}

TY - JOUR

T1 - A Redox Strategy for Light-Driven, Out-of-Equilibrium Isomerizations and Application to Catalytic C-C Bond Cleavage Reactions

AU - Ota, Eisuke

AU - Wang, Huaiju

AU - Frye, Nils Lennart

AU - Knowles, Robert R.

PY - 2019/1/30

Y1 - 2019/1/30

N2 - 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.

AB - 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.

UR - http://www.scopus.com/inward/record.url?scp=85060215165&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85060215165&partnerID=8YFLogxK

U2 - 10.1021/jacs.8b12552

DO - 10.1021/jacs.8b12552

M3 - Article

VL - 141

SP - 1457

EP - 1462

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 4

ER -