TY - JOUR
T1 - Spectroscopic studies of the Chan-Lam amination
T2 - a mechanism-inspired solution to boronic ester reactivity
AU - Vantourout, Julien C.
AU - Miras, Haralampos N.
AU - Isidro-Llobet, Albert
AU - Sproules, Stephen
AU - Watson, Allan J. B.
N1 - This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of the American Chemical Society, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/jacs.6b12800.
PY - 2017/4/5
Y1 - 2017/4/5
N2 - 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.
AB - 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.
KW - Chan-Lam amination reaction
KW - spectroscopy
KW - computational modeling
KW - crystallography
KW - off-cycle inhibitory processes
KW - amines
KW - organoboron reactivity issues
KW - oxidation/protodeboronation side reactions
UR - http://pubs.acs.org/doi/abs/10.1021/jacs.6b12800
U2 - 10.1021/jacs.6b12800
DO - 10.1021/jacs.6b12800
M3 - Article
SN - 0002-7863
VL - 139
SP - 4769
EP - 4779
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 13
ER -