Vantourout, J. C., Miras, H. N. , Isidro-Llobet, A., Sproules, S. and 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), pp. 4769-4779. (doi: 10.1021/jacs.6b12800) (PMID:28266843)
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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.
Item Type: | Articles |
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Additional Information: | This work was supported by the EPSRC. |
Status: | Published |
Refereed: | Yes |
Glasgow Author(s) Enlighten ID: | Sproules, Dr Stephen and Moiras, Professor Haralampos and Watson, Dr Allan |
Authors: | Vantourout, J. C., Miras, H. N., Isidro-Llobet, A., Sproules, S., and Watson, A. J.B. |
College/School: | College of Science and Engineering > School of Chemistry |
Journal Name: | Journal of the American Chemical Society |
Publisher: | American Chemical Society |
ISSN: | 0002-7863 |
ISSN (Online): | 1520-5126 |
Published Online: | 07 March 2017 |
Copyright Holders: | Copyright © 2017 American Chemical Society |
First Published: | First published in Journal of the American Chemical Society 139(13): 4769-4779 |
Publisher Policy: | Reproduced in accordance with the publisher copyright policy |
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