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, including off-cycle inhibitory processes, the source of amine and organoboron reactivity issues, and the origin of competing oxidation/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 language | English |
|---|---|
| Pages (from-to) | 4769-4779 |
| Number of pages | 11 |
| Journal | Journal of the American Chemical Society |
| Volume | 139 |
| Issue number | 13 |
| Early online date | 7 Mar 2017 |
| DOIs | |
| Publication status | Published - 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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-
Allan John Bell Watson
- School of Chemistry - Professor of Homogeneous Catalysis
- Sir James Mackenzie Institute for Early Diagnosis
Person: Academic