Catalytic Ring-Opening of Cyclic Alcohols Enabled by PCET Activation of Strong O-H Bonds

Hatice G. Yayla, Huaiju Wang, Kyle T. Tarantino, Hudson S. Orbe, Robert R. Knowles

Research output: Contribution to journalArticle

113 Scopus citations

Abstract

We report a new photocatalytic protocol for the redox-neutral isomerization of cyclic alcohols to linear ketones via C-C bond scission. Mechanistic studies demonstrate that key alkoxy radical intermediates in this reaction are generated via the direct homolytic activation of alcohol O-H bonds in an unusual intramolecular PCET process, wherein the electron travels to a proximal radical cation in concert with proton transfer to a weak Brønsted base. Effective bond strength considerations are shown to accurately forecast the feasibility of alkoxy radical generation with a given oxidant/base pair.

Original languageEnglish (US)
Pages (from-to)10794-10797
Number of pages4
JournalJournal of the American Chemical Society
Volume138
Issue number34
DOIs
StatePublished - Aug 31 2016

All Science Journal Classification (ASJC) codes

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

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