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.
- Chan-Lam amination reaction
- computational modeling
- off-cycle inhibitory processes
- organoboron reactivity issues
- oxidation/protodeboronation side reactions
Vantourout, J. C., Miras, H. N., Isidro-Llobet, A., Sproules, S., & Watson, A. J. B. (2017). Spectroscopic studies of the Chan-Lam amination: a mechanism-inspired solution to boronic ester reactivity. Journal of the American Chemical Society, 139(13), 4769–4779. https://doi.org/10.1021/jacs.6b12800