Catalytic Alkene Carboaminations Enabled by Oxidative Proton-Coupled Electron Transfer

Gilbert J. Choi, Robert R. Knowles

Research output: Contribution to journalArticlepeer-review

128 Scopus citations

Abstract

Here we describe a dual catalyst system comprised of an iridium photocatalyst and weak phosphate base that is capable of both selectively homolyzing the N-H bonds of N-arylamides (bond dissociation free energies ∼ 100 kcal/mol) via concerted proton-coupled electron transfer (PCET) and mediating efficient carboamination reactions of the resulting amidyl radicals. This manner of PCET activation, which finds its basis in numerous biological redox processes, enables the formal homolysis of a stronger amide N-H bond in the presence of weaker allylic C-H bonds, a selectivity that is uncommon in conventional molecular H atom acceptors. Moreover, this transformation affords access to a broad range of structurally complex heterocycles from simple amide starting materials. The design, synthetic scope, and mechanistic evaluation of the PCET process are described.

Original languageEnglish (US)
Pages (from-to)9226-9229
Number of pages4
JournalJournal of the American Chemical Society
Volume137
Issue number29
DOIs
StatePublished - Jul 29 2015

All Science Journal Classification (ASJC) codes

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

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