Photocatalytic Anti-Markovnikov Hydroamination of Alkenes with Primary Heteroaryl Amines

Eric P. Geunes, Jonathan M. Meinhardt, Emily J. Wu, Robert R. Knowles

Research output: Contribution to journalArticlepeer-review

Abstract

We report a light-driven method for the intermolecular anti-Markovnikov hydroamination of alkenes with primary heteroaryl amines. In this protocol, electron transfer between an amine substrate and an excited-state iridium photocatalyst affords an aminium radical cation (ARC) intermediate that undergoes C-N bond formation with a nucleophilic alkene. Integral to reaction success is the electronic character of the amine, wherein increasingly electron-deficient heteroaryl amines generate increasingly reactive ARCs. Counteranion-dependent reactivity is observed, and iridium triflate photocatalysts are employed in place of conventional iridium hexafluorophosphate complexes. This method exhibits broad functional group tolerance across 55 examples of N-alkylated products derived from pharmaceutically relevant heteroaryl amines.

Original languageAmerican English
Pages (from-to)21738-21744
Number of pages7
JournalJournal of the American Chemical Society
Volume145
Issue number40
DOIs
StatePublished - Oct 11 2023

ASJC Scopus subject areas

  • General Chemistry
  • Biochemistry
  • Catalysis
  • Colloid and Surface Chemistry

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