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

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)

[img]
Preview
Text
139910.pdf - Accepted Version

2MB
[img]
Preview
Text
Suppl_1.pdf - Supplemental Material

4MB
[img]
Preview
Text
Suppl_2.pdf - Supplemental Material

2MB
[img] Text
Suppl_3.txt - Supplemental Material

29kB
[img] Text
Suppl_4.txt - Supplemental Material

16kB

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
Additional Information:This work was supported by the EPSRC.
Status:Published
Refereed:Yes
Glasgow Author(s) Enlighten ID:Sproules, Dr Stephen and Moiras, Dr Charalampos 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

University Staff: Request a correction | Enlighten Editors: Update this record