Spectroscopic studies of the Chan-Lam amination: a mechanism-inspired solution to boronic ester reactivity

Julien C. Vantourout, Haralampos N. Miras, Albert Isidro-Llobet, Stephen Sproules, Allan J. B. Watson

Research output: Contribution to journalArticle

115 Citations (Scopus)
43 Downloads (Pure)

Abstract

We report an investigation of the Chan-Lam amination reaction. A combination of spectroscopy, computational modeling, and crystallography has identified the structures of key intermediates and allowed a complete mechanistic description to be presented, in-cluding off-cycle inhibitory processes, the source of amine and organoboron reactivity issues, and the origin of competing oxida-tion/protodeboronation side reactions. Identification of key mechanistic events has allowed the development of a simple solution to these issues: manipulating Cu(I)→Cu(II) oxidation and exploiting three synergistic roles of boric acid has allowed the development of a general catalytic Chan-Lam amination, overcoming long-standing and unsolved amine and organoboron limitations of this valuable transformation.
Original languageEnglish
Pages (from-to)4769–4779
Number of pages11
JournalJournal of the American Chemical Society
Volume139
Issue number13
Early online date24 Mar 2017
DOIs
Publication statusPublished - 5 Apr 2017

Keywords

  • Chan-Lam amination reaction
  • spectroscopy
  • computational modeling
  • crystallography
  • off-cycle inhibitory processes
  • amines
  • organoboron reactivity issues
  • oxidation/protodeboronation side reactions

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