Catalytic Olefin Hydroamidation Enabled by Proton-Coupled Electron Transfer

David C. Miller, Gilbert J. Choi, Hudson S. Orbe, Robert R. Knowles

Research output: Contribution to journalArticlepeer-review

141 Scopus citations

Abstract

Here we report a ternary catalyst system for the intramolecular hydroamidation of unactivated olefins using simple N-aryl amide derivatives. Amide activation in these reactions occurs via concerted proton-coupled electron transfer (PCET) mediated by an excited state iridium complex and weak phosphate base to furnish a reactive amidyl radical that readily adds to pendant alkenes. A series of H-atom, electron, and proton transfer events with a thiophenol cocatalyst furnish the product and regenerate the active forms of the photocatalyst and base. Mechanistic studies indicate that the amide substrate can be selectively homolyzed via PCET in the presence of the thiophenol, despite a large difference in bond dissociation free energies between these functional groups.

Original languageEnglish (US)
Pages (from-to)13492-13495
Number of pages4
JournalJournal of the American Chemical Society
Volume137
Issue number42
DOIs
StatePublished - Oct 5 2015

All Science Journal Classification (ASJC) codes

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

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