Cu(OTf)2-mediated cross-coupling of nitriles and N-heterocycles with arylboronic acids to generate nitrilium and pyridinium products

Nicola Bell, Chao Xu, Jamie Fyfe, Julien C. Vantourout , Jeremy Brals, Sonia Chabbra, Bela E. Bode, David B. Cordes, Alexandra M. Z. Slawin, Thomas M. McGuire, Allan J. B. Watson

Research output: Contribution to journalArticlepeer-review

10 Citations (Scopus)
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Abstract

Metal‐catalyzed C–N cross‐coupling generally forms C–N bonds by reductive elimination from metal complexes bearing covalent C‐ and N‐ligands. We have identified a Cu‐mediated C–N cross‐coupling that uses a dative N‐ligand in the bond forming event, which, in contrast to conventional methods, generates reactive cationic products. Mechanistic studies suggest the process operates via transmetalation of an aryl organoboron to a Cu(II) complex bearing neutral N‐ligands, such as nitriles or N‐heterocycles. Subsequent generation of a putative Cu(III) complex enables the oxidative C–N coupling to take place, delivering nitrilium intermediates and pyridinium products. The reaction is general for a range of N(sp) and N(sp2) precursors and can be applied to drug synthesis and late‐stage N‐arylation, and the limitations in the methodology are mechanistically evidenced.
Original languageEnglish
Pages (from-to)7935-7940
Number of pages7
JournalAngewandte Chemie International Edition
Volume60
Issue number14
Early online date26 Feb 2021
DOIs
Publication statusPublished - 29 Mar 2021

Keywords

  • Arylation
  • Boron
  • Copper
  • Cross-coupling
  • Mechanism

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