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

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Vantourout, Julien C. and Miras, Haralampos N. and Isidro-Llobet, Albert and Sproules, Stephen and Watson, Allan 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. ISSN 1520-5126 (https://doi.org/10.1021/jacs.6b12800)

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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, 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.

ORCID iDs

Vantourout, Julien C. ORCID logoORCID: https://orcid.org/0000-0002-0602-069X, Miras, Haralampos N., Isidro-Llobet, Albert, Sproules, Stephen and Watson, Allan J. B.;
  • Item type:Article
    ID code:60549
    Dates:
    Date
    Event
    5 April 2017
    Published
    24 March 2017
    Published Online
    16 December 2016
    Accepted
    Notes: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.
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:27 Apr 2017 11:08
    Last modified:18 Dec 2024 11:50
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/60549
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