Bell, N. L. et al. (2021) Cu(OTf)2‐mediated cross‐coupling of nitriles and N‐heterocycles with arylboronic acids to generate nitrilium and pyridinium products. Angewandte Chemie (International Edition), 60(14), pp. 7935-7940. (doi: 10.1002/anie.202016811) (PMID:33449408) (PMCID:PMC8048606)
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Abstract
Metal-catalyzed C–N cross-coupling generally forms C−N bonds by reductive elimination from metal complexes bearing covalent C- and N-ligands. We have identified a Cu-mediated C–N cross-coupling that uses a dative N-ligand in the bond-forming event, which, in contrast to conventional methods, generates reactive cationic products. Mechanistic studies suggest the process operates via transmetalation of an aryl organoboron to a CuII complex bearing neutral N-ligands, such as nitriles or N-heterocycles. Subsequent generation of a putative CuIII complex enables the oxidative C–N coupling to take place, delivering nitrilium intermediates and pyridinium products. The reaction is general for a range of N(sp) and N(sp2) precursors and can be applied to drug synthesis and late-stage N-arylation, and the limitations in the methodology are mechanistically evidenced.
Item Type: | Articles |
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Additional Information: | N.L.B. thanks the EPSRC for postdoctoral funding (EP/R025754/1). C.X. and J.W.B.F. thank the Leverhulme Trust for postdoctoral funding (RPG-2015-308; RPG-2018-362). J.C.V. thanks GlaxoSmithKline for a PhD studentship. J.B. thanks AstraZeneca for a PhD studentship. S.B. thanks the University of St Andrews for a PhD studentship. |
Status: | Published |
Refereed: | Yes |
Glasgow Author(s) Enlighten ID: | Bell, Dr Nicola |
Authors: | Bell, N. L., Xu, C., Fyfe, J. W.B., Vantourout, J. C., Brals, J., Chabbra, S., Bode, B. E., Cordes, D. B., Slawin, A. M.Z., McGuire, T. M., and Watson, A. J.B. |
College/School: | College of Science and Engineering > School of Chemistry |
Journal Name: | Angewandte Chemie (International Edition) |
Publisher: | Wiley |
ISSN: | 1433-7851 |
ISSN (Online): | 1521-3773 |
Published Online: | 15 January 2021 |
Copyright Holders: | Copyright © 2021 The Authors |
First Published: | First published in Angewandte Chemie (International Edition) 60(14): 7935-7940 |
Publisher Policy: | Reproduced under a Creative Commons License |
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